CN114891032A - Monoboron derivative based on fluorene aniline fusion donor, preparation and application thereof - Google Patents
Monoboron derivative based on fluorene aniline fusion donor, preparation and application thereof Download PDFInfo
- Publication number
- CN114891032A CN114891032A CN202210431760.2A CN202210431760A CN114891032A CN 114891032 A CN114891032 A CN 114891032A CN 202210431760 A CN202210431760 A CN 202210431760A CN 114891032 A CN114891032 A CN 114891032A
- Authority
- CN
- China
- Prior art keywords
- group
- fluorene
- reaction
- monoboron
- aniline
- 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
- 230000004927 fusion Effects 0.000 title claims abstract description 92
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical class [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 90
- YXGMOMHGDVQGGS-UHFFFAOYSA-N aniline;9h-fluorene Chemical compound NC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 YXGMOMHGDVQGGS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 64
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 53
- 229910052796 boron Inorganic materials 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 125000004429 atom Chemical group 0.000 claims abstract description 35
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 64
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 41
- -1 9, 9-dimethylfluorenyl Chemical group 0.000 claims description 39
- 239000003446 ligand Substances 0.000 claims description 32
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 25
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 22
- 150000002367 halogens Chemical class 0.000 claims description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000002585 base Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 150000004820 halides Chemical class 0.000 claims description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001555 benzenes Chemical class 0.000 claims description 8
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- IMGFFZATJWHYPA-UHFFFAOYSA-N 10-phenylspiro[acridine-9,9'-fluorene] Chemical group C1=CC=CC=C1N1C2=CC=CC=C2C2(C3=CC=CC=C3C3=CC=CC=C32)C2=CC=CC=C21 IMGFFZATJWHYPA-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 4
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Chemical group 0.000 claims description 4
- 239000011630 iodine Chemical group 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 125000003003 spiro group Chemical group 0.000 claims description 4
- QQNLHOMPVNTETJ-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene] Chemical group C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QQNLHOMPVNTETJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- QPUXWYMXZRSKOF-UHFFFAOYSA-N 9,9-dimethylspiro[anthracene-10,9'-fluorene] Chemical group C12=CC=CC=C2C(C)(C)C2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QPUXWYMXZRSKOF-UHFFFAOYSA-N 0.000 claims description 3
- GNFUAYSHEQURLP-UHFFFAOYSA-N C1=CC=C(C=C1)C2(C3=CC=CC=C3C4(C5=CC=CC=C5C6=CC=CC=C64)C7=CC=CC=C72)C8=CC=CC=C8 Chemical group C1=CC=C(C=C1)C2(C3=CC=CC=C3C4(C5=CC=CC=C5C6=CC=CC=C64)C7=CC=CC=C72)C8=CC=CC=C8 GNFUAYSHEQURLP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 3
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 229920003026 Acene Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 6
- 150000001875 compounds Chemical class 0.000 description 54
- 239000002019 doping agent Substances 0.000 description 35
- 238000005401 electroluminescence Methods 0.000 description 35
- 239000010410 layer Substances 0.000 description 35
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- 238000000921 elemental analysis Methods 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000543 intermediate Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 16
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 15
- 239000013078 crystal Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- SDTHIDMOBRXVOQ-UHFFFAOYSA-N 5-[bis(2-chloroethyl)amino]-6-methyl-1h-pyrimidine-2,4-dione Chemical compound CC=1NC(=O)NC(=O)C=1N(CCCl)CCCl SDTHIDMOBRXVOQ-UHFFFAOYSA-N 0.000 description 9
- 230000021615 conjugation Effects 0.000 description 9
- 238000004949 mass spectrometry Methods 0.000 description 9
- 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 8
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 8
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 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 7
- YRRHZIUXMLLOSI-UHFFFAOYSA-N aniline;9h-fluorene Chemical compound NC1=CC=CC=C1.NC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 YRRHZIUXMLLOSI-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
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- 238000004467 single crystal X-ray diffraction Methods 0.000 description 6
- XFWGSCNZZYLJJG-UHFFFAOYSA-N 4-bromo-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C=CC=C2Br XFWGSCNZZYLJJG-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000004808 supercritical fluid chromatography Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 3
- 150000001638 boron Chemical class 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical group C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XRDGVCAFKJOSLC-UHFFFAOYSA-N N-phenyl-9H-fluoren-4-amine Chemical compound N(C1=CC=CC=C1)C1=CC=CC=2CC3=CC=CC=C3C1=2 XRDGVCAFKJOSLC-UHFFFAOYSA-N 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005567 fluorenylene group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 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 1
- DZHFFMWJXJBBRG-UHFFFAOYSA-N 1-bromo-3,5-dichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Br)=C1 DZHFFMWJXJBBRG-UHFFFAOYSA-N 0.000 description 1
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical group C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- BKQXUNGELBDWLS-UHFFFAOYSA-N 9,9-diphenylfluorene Chemical group C1=CC=CC=C1C1(C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 BKQXUNGELBDWLS-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JEEHCWMEXMRCDS-UHFFFAOYSA-N bis(9H-fluoren-9-yl)methanone Chemical group C12=CC=CC=C2C2=CC=CC=C2C1C(=O)C1C2=CC=CC=C2C2=CC=CC=C21 JEEHCWMEXMRCDS-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical group COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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Images
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 System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- 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
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Abstract
The invention belongs to the field of preparation and application of organic photoelectric materials, and discloses a monoboron derivative based on a fluorene aniline fusion donor, and preparation and application thereof, wherein the monoboron derivative has a general structure shown as at least one of general formulas A-1 to A-3; wherein the R group is selected from: a fluorene or fluorene derivative group having 13 to 38 carbon atoms; and, for the general formulae A-2 and A-3, the R group is bonded to the boron atom, the bonding atom is the carbon atom at the 3-position thereof, and the nitrogen atom is bonded to the carbon atom at the 4-position thereof in the general formulae. The monoboron derivative based on the fluorene aniline fusion donor can realize the FWHM below 30nm based on the B-N resonance effect, and can effectively improve OLED devicesThe color purity of (2).
Description
Technical Field
The invention belongs to the field of preparation and application of organic photoelectric materials, and particularly relates to a mono-boron derivative based on a fluorene aniline fusion donor, and preparation and application thereof.
Background
Organic electroluminescence (OLED) technology has been widely used in the display field due to its outstanding advantages of self-luminescence, fast response speed, flexibility and foldability. Meanwhile, with the continuous development of related technologies of OLEDs and the continuous improvement of product performance requirements of consumers, the conventional organic light-emitting materials generally face the problem of excessively wide full width at half maximum (FWHM) (70-100 nm) of emission spectra, so that the OLEDs cannot directly realize high color purity and wide color gamut display, and a corresponding solution is urgently needed.
The third generation of Thermally Activated Delayed Fluorescence (TADF) realizes 100% internal quantum efficiency in small organic molecules, is expected to replace the existing traditional fluorescent materials and phosphorescent luminescent materials, and has advantages in cost and efficiency. However, due to the molecular design of the TADF material, the TADF material generally has a strong structural relaxation property, so that the full width at half maximum (FWHM) of the light emission spectrum of the TADF material is generally over 70nm, and the color purity of the OLED device is greatly influenced. To solve this problem, professor t.hatakeyama et al, university of the academy of western sciences, developed a thermally-induced delayed fluorescent material (MR-TADF) with multiple induced resonance characteristics, whose principle is to achieve separation of molecules HOMO/LUMO on an atomic scale by the opposite resonance effect of electron-deficient atom (B) and electron-rich atom (N), thereby achieving an extremely narrow FWHM while maintaining the characteristics of the TADF material. However, most of the currently reported MR-TADF molecules adopt simple donors to construct resonance frameworks, and the types of materials are limited. The sensitization strategy for effectively improving the performance of the device at the present stage also faces the problems of large difference of physical and chemical properties between the sensitizer material and the luminescent object, less combination of high matching degree and the like. Therefore, MR-TADF isomers with similar molecular structures and similar physical and chemical properties are developed to build a self-sensitized luminescent material system to improve the comprehensive performance of the OLED, and the OLED has great scientific and technological value and industrial application prospect.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a class of monoboron derivatives based on fluorene and aniline fusion donors, and preparation and application thereof, wherein a simple group donor is modified, a rigid group fluorene derivative is introduced on the basis of reserving electron-rich N atoms to form a new fusion donor in a combined manner, the fusion donor based on fluorene and aniline has the characteristics of rigidity and large volume, the electron supply capability of the fusion donor is slightly stronger than that of a parent group diphenylamine of the fusion donor, the group is introduced into an MR-TADF molecular system as a novel electron-rich group, the monoboron derivative based on the fluorene and aniline fusion donor can be obtained, the FWHM below 30nm can be realized based on the B-N resonance effect, and the color purity of an OLED device can be effectively improved; meanwhile, the fluorene skeleton extending from the fluorene fusion donor can realize conjugate regulation and control at different closed loop positions, so that gradient red shift of light color is obtained, and when the fluorene skeleton is used as a luminescent material applied to an organic electroluminescent device, energy transfer between isomers can be realized, and higher device efficiency is obtained. In addition, the thermal stability of the material is remarkably improved due to the enhancement of the rigidity of the monoboron derivative of the fluorene group aniline fusion donor.
To achieve the above object, according to one aspect of the present invention, there is provided a monoboron derivative based on a fluorene-based oaniline fusion donor, characterized in that the monoboron derivative has a general structure represented by at least one of general formula a-1 to general formula a-3:
wherein the R group is selected from: a fluorene group or a fluorene derivative group having 13 to 38 carbon atoms;
and, for formulas A-2 and A-3, the R group is bonded to the boron atom in the formula, the bonding atom is the carbon atom at position 3 of the R group, and the nitrogen atom is bonded to the carbon atom at position 4 of the R group.
As a further preference of the invention, the monoboron derivative is prepared from an intermediate, the intermediate has a general formula structure shown as a formula A, and the target product is three stereoisomeric monoboron derivatives having general formula structures shown as formulas A-1 to A-3;
as a further preference of the present invention, the R group is fluorenyl;
or the R group is 9, 9-dimethylfluorenyl;
or the R group is 9, 9-diphenyl fluorenyl;
or the R group is 9-fluorenone;
or, the R group is 9, 9' -spirobifluorenyl;
or, the R group is dibenzofuranyl;
or, the R group is dibenzothienyl;
or the R group is spiro [ fluorene-9, 9' -xanthene ] group;
or the R group is spiro [ fluorene-9, 9' -thiaanthracene ] group;
or the R group is 10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] group;
or the R group is 10, 10-dimethyl-10H-spiro [ anthracene-9, 9' -fluorene ] group;
or the R group is 10, 10-diphenyl-10H-spiro [ anthracene-9, 9' -fluorene ] group.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned monoboron derivative based on a fluorene-based oaniline fusion donor, comprising the steps of:
(1) 1,3, 5-trihalo substituted benzene is used as a raw material and is matched with a raw material diphenylamine to carry out Buchwald-Hartwig reaction to obtain a 3, 5-dihalo triphenylamine compound;
(2) taking a halide R-X corresponding to the R group as a raw material, matching with aniline as a raw material, and carrying out a C-N coupling reaction on the halide R-X and the aniline through palladium catalysis to obtain a fluorene aniline fusion donor containing the R group; wherein, for the halide corresponding to the R group, the halogen X is positioned at the No. 4 site of the R group; the halogen X is fluorine, chlorine, bromine or iodine;
(3) taking the 3, 5-dihalogen triphenylamine compound obtained in the step (1) and the fluorene group-containing aniline fusion donor obtained in the step (2) as raw materials, and carrying out C-N coupling reaction on the raw materials under the catalysis of palladium to obtain an intermediate shown in a general formula A;
(4) using halogen substituent BX of boron for the intermediate obtained in the step (3) 3 A borohybrid-Krafft Reaction (Tandem Bora-Friedel-Crafts Reaction) occurs, resulting in a monoboron derivative based on a fluorene rylamine fusion donor; wherein, the halogen substituent BX of the boron 3 In particular to boron trichloride BCl 3 Boron tribromide BBr 3 Or boron triiodide BI 3 。
As a further preferred aspect of the present invention, in the step (1), the C-N coupling reaction is performed in a solvent system in the presence of a ligand and a base, specifically, the 1,3, 5-trihalo-substituted benzene raw material, the diphenylamine raw material, the palladium catalyst, the ligand, the base and the solvent are mixed in such an amount that the volume ratio of the five substances of the 1,3, 5-trihalo-substituted benzene raw material, the diphenylamine raw material, the palladium catalyst, the ligand and the base to the solvent is 1mmol:1mmol:0.01-0.03mmol:0.03-0.05mmol:3-5mmol:5 to 10ml of the mixture is added into a reaction device, then blowing out air by using nitrogen, heating to a reflux state under the protection of nitrogen, reacting for 8-48 hours, cooling to room temperature after complete reaction, and carrying out purification post-treatment to obtain a 3, 5-dihalogen triphenylamine compound;
wherein, the halogens at the 1 position, the 3 position and the 5 position in the 1,3, 5-trihalo-substituted benzene are selected from fluorine, chlorine, bromine and iodine, and the reaction activity of the halogen at the 1 position is higher than that at the 3 position and the 5 position; the ligand is a phosphine-containing ligand, preferably tri-tert-butylphosphine tetrafluoroborate (t-Bu) 3 PHBF 4 ) (ii) a The base is an organic base, preferably sodium tert-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is preferably tris-dibenzylideneacetone dipalladium.
As a further preferable aspect of the present invention, in the step (2), the C-N coupling reaction is performed in a solvent system in the presence of a ligand and a base, specifically, the halide raw material, the aniline raw material, the palladium catalyst, the ligand, the base and the solvent corresponding to the R group are added into a reaction apparatus according to the amount of the halide raw material, the aniline raw material, the palladium catalyst, the ligand and the base and the volume ratio of the solvent being 1mmol:1-2mmol:0.01-0.03mmol:0.03-0.05mmol:3-5mmol:5-10ml, then air is blown off by using nitrogen, the mixture is heated to a reflux state under the protection of nitrogen for reaction for 8-48 hours, and after the reaction is completed, the mixture is cooled to room temperature for purification and post-treatment, so as to obtain a fluorene and aniline fusion donor containing the R group;
wherein the ligand is a phosphine-containing ligand, preferably tri-tert-butylphosphine tetrafluoroborate (t-Bu) 3 PHBF 4 ) (ii) a The base is an organic base, preferably sodium tert-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is preferably tris-dibenzylideneacetone dipalladium.
In the step (3), the C-N coupling reaction is carried out in a solvent system in the presence of a ligand and a base, specifically, the amount of five substances, namely 3, 5-dihalotriphenylamine compound raw material, R-group-containing fluorene-aniline fusion donor raw material, palladium catalyst, ligand, base and solvent, is 1mmol:2-2.5mmol:0.02-0.05mmol:0.05-0.10mmol:3-6mmol:6-15ml, based on the volume ratio of 3, 5-dihalotriphenylamine compound raw material, R-group-containing fluorene-aniline fusion donor raw material, palladium catalyst, ligand and base, the reaction device is purged with nitrogen gas, heated to a reflux state under the protection of nitrogen gas for 12-60 hours, cooled to room temperature after the reaction is completed, purified, obtaining an intermediate shown as a general formula A;
wherein the ligand is a phosphine-containing ligand, preferably 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (SPhos); the base is an organic base, preferably sodium tert-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is palladium acetate (Pd (OAc) 2 )。
As a further preferred aspect of the present invention, the step (4) is specifically: vacuum drying the intermediate at 80-120 deg.C for 8-24 hr before reaction, dissolving the intermediate in o-dichlorobenzene (o-DCB) solvent, ultrasonic treating to dissolve completely, blowing off nitrogen, stirring at room temperature under nitrogen protection, and slowly adding BX dropwise at a temperature lower than room temperature 3 After the dropwise addition, heating the reaction system to 150-250 ℃, and stirring for reaction for 20-48 hours; cooling to room temperature, placing the system in ice bath, keeping at below 0 deg.C, adding N.N-Diisopropylethylamine (DIPEA), reacting for 1-5 hr, and reducing pressureDistilling to remove the solvent, and then performing column chromatography separation and purification to obtain the monoboron derivative with the general structure shown as the general formula A-1 to the general formula A-3;
wherein the amount of substance of the intermediate, the volume of the ortho-dichlorobenzene, the BX 3 The ratio of the amount of said substance of N.N-Diisopropylethylamine (DIPEA) to the amount of said substance of N.N-Diisopropylethylamine (DIPEA) satisfies 1mmol:10-30ml:1.5-24mmol:12-18 mmol.
According to another aspect of the present invention, the present invention provides the use of the above-mentioned monoboron derivative based on a fluorene and aniline fusion donor in a light emitting layer of an organic electroluminescent device;
preferably, the organic electroluminescent device comprises in sequence: the light-emitting diode comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode;
more preferably, an exciton blocking layer is further disposed between the hole transport layer and the light emitting layer; an exciton blocking layer is also disposed between the light emitting layer and the electron transport layer.
As a further preferred aspect of the present invention, the mono-boron derivative based on the fluorene and aniline fusion donor is specifically applied as a guest light emitting material in a light emitting layer of an organic electroluminescent device.
In a further preferred embodiment of the present invention, the monoboron derivative has a general structure represented by two or three of general formulae A-1 to A-3.
Through the technical scheme, compared with the prior art (especially compared with a reported MR-TADF compound), the single boron derivative of the fluorene aniline fusion donor has multiple induced resonance effect and thermal delayed fluorescence characteristics, can realize the half-peak width narrowing of a luminescent spectrum and high-efficiency fluorescence emission, is used as an organic fluorescence luminescent material applied to a luminescent layer structure of an organic electroluminescent device (OLED), and is beneficial to improving the luminescent color purity of the OLED. In the invention, the monoboron derivative based on the same R group has three isomer configurations which are three stereoisomers with conjugated extensions of different degrees, so that the photochromic has the characteristic of gradient red shift of the luminescence peak wavelength, particularly three or two isomer materials can be co-mixed, and the gradient energy transfer is realized through the self-sensitization effect, thereby being beneficial to improving the exciton utilization efficiency and improving the overall performance of the electroluminescent device.
According to the invention, the resonance core skeleton of the fluorene fusion donor type MR-TADF molecule is regulated and controlled through different B atom closed-loop positions, when the B atom is closed-loop between the amino benzene ring of the fluorene and aniline fusion donor and the benzene ring of diphenylamine (namely the compound represented by the general formula A-1), the resonance skeleton of the monoboron derivative is similar to that of the conventional MR-TADF, does not obtain conjugated extension, and the light color is in the range of 440-460 nm; when the B atom is closed between the amino benzene ring of the fluorene-aniline fusion donor and the No. 3 position of the amino fluorene ring of the other fluorene-aniline fusion donor (i.e. the compound represented by the general formula A-2), the resonance skeleton of the monoboron derivative extends in a conjugated manner, and the light color of the monoboron derivative is in a red shift range of 460-480 nm; when the B atom is closed between the 3-position of the aminofluorene ring of the two fluorene and aniline fusion donors (i.e. the compound represented by the general formula A-3), the conjugation of the resonance skeleton of the monoboron derivatives is further extended, and the light color of the monoboron derivatives is continuously red-shifted and is in the range of 480-500 nm. The invention realizes the gradient red shift regulation of the light color of MR-TADF molecules of three stereoisomers of the same R group, and can be obtained through the following embodiments: the fluorene fusion donor type MR-TADF compounds 1-1, 2-1 to 12-1 contained in the general formula A-1 have the light-emitting wavelength in the deep blue region and the light-emitting peak value of 440-460 nm; the fluorene fused donor type MR-TADF compounds 1-2, 2-2 to 12-2 contained in the general formula A-2 have the light-emitting wavelength in the pure blue region and the light-emitting peak value of 460-480 nm; the fluorene fusion donor type MR-TADF compounds 1-3, 2-3 to 12-3 contained in the general formula A-3 have light-emitting wavelengths in the sky blue region and have light-emitting peak values of 480-500 nm.
Specifically, the present invention can achieve the following advantageous effects:
(1) the resonance core of the monoboron derivative based on the fluorene aniline fusion donor can extend outwards, and the electron cloud distribution is more delocalized. A novel MR-TADF luminescent molecule system is expanded by adopting fluorene fusion donors, and meanwhile, the introduction of rigid groups is beneficial to further inhibiting the vibration relaxation in the excited state of the molecule to narrow the luminescent spectrum, reducing the non-radiative energy loss approach and improving the exciton utilization efficiency.
(2) The fluorene based and aniline fused donor has slightly stronger electron supplying capacity than diphenylamine (original parent group of the fluorene based and aniline fused donor), so that the closed loop position can be ensured to be carried out according to the target requirement during the boronization reaction, and the required three monoboron derivatives with different framework extensions and light color gradient red shift and stereoisomerism are generated. In addition, the synthesis process is simple and easy to implement, and is beneficial to large-scale industrial production.
(3) The same R group of the monoboron derivative based on the fluorene aniline fusion donor has three isomers, the three stereoisomers have similar structures and similar properties, and the high-performance mixed component matching is easier to realize in industrial application to prepare devices, thereby being beneficial to simplifying the preparation process and reducing the cost. Besides independently selecting one of the single boron derivatives as a luminescent client, two or three stereoisomeric single boron derivatives can be selected to be blended as a luminescent material according to the requirement on light color to be applied to an OLED device, and the stability and reliability of the electroluminescent device are improved by utilizing the self-sensitization characteristic realized by energy transfer among materials.
(4) In addition, for three kinds of monoboron derivatives based on fluorene aniline fusion donors with the same R group, because the gradient of the conjugation degree of the derivatives is increased (wherein the conjugation degree of the general formula A-1 is minimum, the conjugation degree of the general formula A-3 is maximum, and the general formula A-2 is positioned between the two), energy transfer from low conjugation to high conjugation monoboron derivatives exists in a doped film or an electroluminescent device prepared by blending two or three kinds of monoboron derivatives; therefore, when the kind of the R group is fixed, in addition to applying the monoboron derivative satisfying one of the general formulas A-1, A-2 and A-3 to the light emitting layer in the organic electroluminescent device, the present invention can also apply the monoboron derivative satisfying two or even three of the general formulas A-1, A-2 and A-3 (i.e., a mixture of two or three monoboron derivatives having isomers) to the light emitting layer in the organic electroluminescent device, and can further improve the device performance.
Drawings
Fig. 1 is a schematic structural diagram of an electroluminescent device.
Fig. 2 is a mechanism diagram of a three-component mixed system energy transfer process constructed by using the monoboron derivative of the fluorene-aniline fusion donor of the present invention as a luminescent guest material.
FIG. 3 is a single crystal analysis diagram of Compound 1-1 to Compound 5-3.
FIG. 4 is a graph comparing the thermal decomposition temperatures of compounds 1-1, 2-1, 3-3, 5-3 with conventional MR-TADF compound PAB.
Fig. 5 is an external quantum efficiency versus current density characteristic of the three-component self-sensitized devices of device examples 1 to 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In general, the monoboron derivative based on the fluorene and aniline fusion donor in the invention has a general structure shown in formula A, and the monoboron derivative has a general structure shown in at least one of general formulas A-1 to A-3 (two R groups in any general formula are the same group):
wherein the R group is selected from: a fluorene group or a fluorene derivative group having 13 to 38 carbon atoms; for the R group position: when it is bonded to a boron atom in the formula (specifically, formulae A-2 and A-3), the bonding atom is the carbon atom at position 3 of the R group, and the nitrogen atom is bonded to the carbon atom at position 4 of the R group.
The R group may be a fluorene group or a fluorene derivative group, such as a fluorenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-fluorenone group, 9 '-spirobifluorenyl group, dibenzofuranyl group, dibenzothienyl group, spiro [ fluorene-9, 9' -xanthene ] group, spiro [ fluorene-9, 9 '-thiaanthracene ] group, 10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] group, 10-dimethyl-10H-spiro [ anthracene-9, 9 '-fluorene ] group, 10-diphenyl-10H-spiro [ anthracene-9, 9' -fluorene ] group, and the like.
Taking the intermediate structural formulas as formula 1 to formula 12 as examples, the intermediates can correspond to 12 classes of 36 monoboron derivative compounds. Wherein, the formulas 1-1 to 12-3 correspond to monoboron derivatives of 36 fluorene aniline fusion donors, and concretely:
in the formula 1 and the formulas 1-1 to 1-3, R is fluorenyl;
in the formula 2 and the formulae 2-1 to 2-3, R is 9, 9-dimethylfluorenyl;
in the formula 3 and the formulae 3-1 to 3-3, R is 9, 9-diphenylfluorenyl;
in the formula 4 and the formulae 4-1 to 4-3, R is 9-fluorenylketone group;
in the formula 5 and the formulae 5-1 to 5-3, R is 9, 9' -spirobifluorenyl.
In the formula 6 and the formulae 6-1 to 6-3, R is dibenzofuranyl.
In the formula 7 and the formulae 7-1 to 7-3, R is dibenzothienyl.
In the formula 8, and the formulae 8-1 to 8-3, R is a spiro [ fluorene-9, 9' -xanthene ] group.
In the formula 9, the formulae 9-1 to 9-3, R is a spiro [ fluorene-9, 9' -thiaanthracene ] group.
In the formula 10, the formulae 10-1 to 10-3, R is a 10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] group.
In the formula 11 and the formulae 11-1 to 11-3, R is 10, 10-dimethyl-10H-spiro [ anthracene-9, 9' -fluorene ] group.
In the formula 12 and the formulae 12-1 to 12-3, R is 10, 10-diphenyl-10H-spiro [ anthracene-9, 9' -fluorene ] group.
The specific intermediate and monoboron derivative compounds have the following structural formulas:
accordingly, the preparation method of the monoboron derivative of the fluorene aniline fusion donor comprises the following steps:
(1) 1,3, 5-trihalobenzene (the halogen at the 1,3 and 5 positions is selected from fluorine, chlorine, bromine and iodine, and the reaction activity of the halogen at the 1 position is higher than that of the halogen at the 3 and 5 positions) is used as a raw material, and Buchwald-Hartwig reaction is carried out by matching with diphenylamine to obtain a 3, 5-dihalotriphen compound (the Buchwald-Hartwig reaction can be controlled only aiming at the halogen at the 1 position in the 1,3, 5-trihalobenzene by strictly controlling the proportion of the reaction raw materials; the prior art knows that the reaction activity strictly follows the activity sequence of the halogen such as iodine, bromine, chlorine and fluorine);
(2) taking a halide R-X corresponding to the R group as a raw material, matching with aniline as a raw material, and carrying out a C-N coupling reaction on the halide R-X and the aniline through palladium catalysis to obtain a fluorene aniline fusion donor containing the R group; wherein, for the halide corresponding to the R group, the halogen X is positioned at the No. 4 position of the R group; the halogen X is fluorine, chlorine, bromine or iodine;
(3) taking the 3, 5-dihalogen triphenylamine compound obtained in the step (1) and the fluorene group-containing aniline fusion donor obtained in the step (2) as raw materials, and carrying out C-N coupling reaction on the raw materials under the catalysis of palladium to obtain an intermediate shown in a general formula A;
(4) using halogen substituted compound BX of boron for the intermediate obtained in the step (3) 3 (X represents halogen, BX) 3 Namely boron trichloride, boron tribromide, boron triiodide) to undergo a borohybrid-krafts Reaction (Tandem Bora-Friedel-Crafts Reaction), thereby obtaining a monoboron derivative based on a fluorene-based acenylamine fusion donor.
In some synthesis examples, the specific processes involved in steps (1), (2) and (3) may be bromine or iodine-containing material and aniline material, and the palladium catalyst is selected from bis (Pd) tris (dibenzylideneacetone) 2 (dba) 3 ) The ligand is tri-tert-butylphosphine tetrafluoroborate, the base is sodium tert-butoxide, and the solventSelecting dry toluene, adding the bromo-or iodo-raw material, aniline-raw material, tris-dibenzylideneacetone dipalladium, tris-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide and toluene into a reaction device according to the mass or volume ratio (toluene) of 1mmol:1-2mmol:0.01-0.03mmol:0.03-0.05mmol:3-5mmol:5-10ml (such as 1mmol:1mmol:0.01mmol:0.03mmol:3mmol:6ml), blowing air (such as 15 min) by using nitrogen, heating to a reflux state under the protection of nitrogen for reaction for 8-48 h (such as 12 h), cooling to room temperature after the thin-layer chromatography detection reaction is complete, and carrying out post-treatment purification operation to obtain the compounds in the steps (1), (2) and (3).
Or: the specific process involved may be that the chloro-or fluoro-containing raw material and the fluorenylene fusion donor material containing R group, the reactivity of chlorine and fluorine is reduced, the palladium catalyst is changed to palladium acetate, the ligand is changed to 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, the rest is kept unchanged, the chloro-or fluoro-containing raw material, the fluorenylene fusion donor material containing R group, palladium acetate, 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, sodium tert-butoxide and toluene are added into the reaction device according to the amount of substance or volume ratio (toluene) of 1mmol:2-2.5mmol:0.02-0.05mmol:0.05-0.10mmol:3-6mmol:6-15ml (e.g., 1mmol:2mmol:0.02mmol:0.05mmol:3mmol:6ml), nitrogen is used to blow air (e.g. 15 min), and then heating to a reflux state under the protection of nitrogen for reaction for 12-60 hours (for example, 18-24 hours), detecting the reaction by thin-layer chromatography, cooling to room temperature after the reaction is completed, and carrying out post-treatment purification operation to obtain the intermediate of the stereoisomeric type monoboron derivative based on the fluorene acene amine fusion donor.
In some synthetic embodiments, the step (4) may specifically be: the specific process involved is to dry the intermediate of the monoboron derivative of the fluorene and aniline fusion donor in vacuum at 80-120 deg.C (e.g. 120 deg.C) for 8-24 hours (e.g. 10 hours) before reaction, then dissolve the intermediate in o-dichlorobenzene solvent, dissolve it completely by ultrasonic treatment, blow off nitrogen (e.g. 30 minutes), then stir at room temperature for 30 minutes under nitrogen protection, slowly add BX dropwise at below 25 deg.C 3 After the dripping is finished, the temperature of the system is programmed to 150-250 ℃ (such as 180-200 ℃), and the stirring is carried outStirring for reaction for 20-48 hours (such as 20-24 hours), cooling to room temperature, placing the system in an ice bath, keeping the temperature at 0 ℃, adding N, N-Diisopropylethylamine (DIPEA), reacting for 1-5 hours (such as 2 hours), removing the solvent by reduced pressure distillation, and then carrying out column chromatography separation and purification to obtain three monoboron derivatives based on fluorene aniline fusion donors; wherein the amount of substance of an intermediate of a monoboron derivative of the fluorenylanilide fusion donor, the volume of o-dichlorobenzene, the BX 3 The feed ratio of the amount of substance(s) of (a) and the amount of substance(s) of said N.N-Diisopropylethylamine (DIPEA) is 1mmol:10-30ml:1.5-24mmol:12-18mmol (e.g., 1mmol:20ml:2-4mmol:15-18 mmol).
In addition, similar to the conventional treatment in the prior art, in the synthetic example, the eluent for column chromatography is cyclohexane or a mixed solution of cyclohexane and dichloromethane in different volume ratios. The benign solvent of the system selected for recrystallization is dichloromethane and toluene, and the poor solvent is methanol and cyclohexane.
The following are synthetic examples:
synthesis example 1: the compounds 1-1 to 1-3 of the present invention can be synthesized by the following methods:
(1) 1-bromo-3, 5-dichlorobenzene (20g,88.5mmol), diphenylamine (15.0g,88.5mmol), tris-dibenzylideneacetone dipalladium (0.82g,0.89mmol), tri-tert-butylphosphine tetrafluoroborate (0.77g,2.66mmol), sodium tert-butoxide (25.5g,265.5mmol) and dry toluene (200mL) were added to a 500mL three-necked flask, purged with nitrogen for 15 minutes, heated to 120 ℃ in a nitrogen atmosphere, refluxed and stirred for reaction for 12 hours, after the reaction was complete, cooled to room temperature, extracted with dichloromethane and water to collect the organic layer, dried, concentrated, column chromatographed for primary purification, and the crude product was further recrystallized with dichloromethane and methanol to give 3, 5-dichloro-triphenylamine as a white solid powder, 27.3g, 98.5% yield.
(2) 4-bromofluorene (15g,61.5mmol), aniline (5.8g,61.5mmol), tris-dibenzylideneacetone dipalladium (0.57g,0.62mmol), tri-tert-butylphosphine tetrafluoroborate (0.54g,1.85mmol), sodium tert-butoxide (17.7g,184.5mmol) and dry toluene (200mL) were added to a 500mL three-necked flask, purged with nitrogen for 15 minutes, heated to 120 ℃ in a nitrogen atmosphere, refluxed and stirred for reaction for 12 hours, after the reaction was completed, cooled to room temperature, extracted and collected with dichloromethane and water, dried, concentrated, subjected to column chromatography for preliminary purification, and the crude product was further recrystallized using dichloromethane and methanol to obtain N-phenyl-9H-fluoren-4-amine as a white solid powder, 14.6g, with a yield of 92.1%.
(3) Then, N-phenyl-9H-fluoren-4-amine (14.6g,56.8mmol), 3, 5-dichloro-triphenylamine (8.8g,28.4mmol), palladium acetate (0.13g,0.57mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (0.70g,1.71mmol), sodium tert-butoxide (16.4g,170.4mmol), and dry toluene (200mL) were added to a 500mL three-necked flask, purged with nitrogen for 15 minutes, then heated to 120 ℃ in a nitrogen atmosphere, refluxed and stirred for reaction for 20 hours, after completion of the reaction, cooled to room temperature, extracted with dichloromethane and water to collect the organic layer, dried and concentrated, purified by column chromatography, and the crude product was further recrystallized using dichloromethane and methanol to give compound 1, 18.2g as a white solid powder, with a yield of 84.7%.
(4) Compound 1(10.0g,13.2mmol) is dried in vacuum in advance and then dissolved in 200ml o-dichlorobenzene by ultrasound, air is pumped out by an oil pump repeatedly, then 3.82ml boron tribromide is slowly dripped below 25 ℃ in nitrogen environment, the mixture is heated to 180 ℃ for reflux stirring reaction for 24 hours, after the reaction is completed, the mixture is cooled to 0 ℃, 32.7ml N.N-Diisopropylethylamine (DIPEA) is added, then the mixture is kept at 0 ℃ for stirring reaction for 2 hours, after the reaction is completed, the o-dichlorobenzene is removed by reduced pressure distillation, concentrated mother liquor is collected, column chromatography is carried out for preliminary purification (eluent is cyclohexane), crude products are further recrystallized by toluene and methanol to obtain light yellow solid powder which is a mixture of three stereoisomers of 1-1, 1-2 and 1-3, the yield is 6.7g and 66.8%, then the mixture is further analyzed by supercritical fluid chromatography (reversed phase column, methanol and water in a volume ratio of 95:5, the same below) in a ratio of 3:4:3 (mass ratio, the same below), and the spatial structures of the three isomers were confirmed by single crystal analysis, as shown in fig. 3, in which different positions of the B atom and the N atom are indicated, and the structures of the three isomers were judged by the closed-loop position of the B atom.
Compound 1-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 763.3159, test value: 764.5170. elemental analysis results: theoretical value: 88.07 percent of C; 5.02 percent of H; b, 1.42 percent; and 5.50 percent of N. Experimental values: 88.10 percent of C; 4.96 percent of H; b, 1.41 percent; and 5.54 percent of N. From the mass spectrum, the element analysis result and the single crystal structure analysis (figure 3), the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is a target compound 1-1. The material has good thermal stability, and the decomposition temperature reaches more than 460 ℃.
Compounds 1-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 763.3159, test value: 764.3192. elemental analysis results: theoretical value: 88.07 percent of C; 5.02 percent of H; b, 1.42 percent; and 5.50 percent of N. Experimental values: 88.04 percent of C; 4.99 percent of H; b, 1.45 percent; and 5.53 percent of N. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 1-2. The material has good thermal stability, and the decomposition temperature reaches more than 460 ℃.
Compounds 1-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 763.3159, test value: 764.2597. elemental analysis results: theoretical value: 88.07 percent of C; 5.02 percent of H; b, 1.42 percent; and 5.50 percent of N. Experimental values: 88.09 percent of C; 4.99 percent of H; b, 1.41 percent; and 5.52 percent of N. From the mass spectrum and the elemental analysis results and the single crystal structure analysis (figure 3), it can be known that the closed ring position of the B atom is on the fluorene group of the two fusion donors, and the product has a correct structure and is a target compound 1-3. The material has good thermal stability, and the decomposition temperature reaches more than 470 ℃.
Synthesis example 2: the compounds 2-1 to 2-3 of the present invention can be synthesized by the following methods:
this example is substantially the same as synthetic example 1 except that: in this example, 4-bromofluorene needs to be replaced by the bromide at the 4-position of 9, 9-dimethylfluorene in equal amount, and the rest conditions are kept unchanged. Finally, bright yellow solid powder which is a mixture of three stereoisomers 2-1, 2-2 and 2-3 and is 8.1g is obtained, the yield is 74.9%, then the three stereoisomers are further analyzed by supercritical fluid chromatography in a ratio of 3:5:2, the spatial structures of the three isomers can be confirmed by single crystal analysis, as shown in the attached figure 3, different positions of a B atom and an N atom are indicated in the figure, and the structures of the three isomers can be judged by the closed-loop position of the B atom.
Compound 2-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 819.3785, test value: 820.3818. elemental analysis results: theoretical value: 87.90 percent of C; 5.66 percent of H; b, 1.32 percent; and 5.13 percent of N. Experimental values: 87.96 percent of C; 5.63 percent of H; 1.33 percent of B; and 5.09 percent of N. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (figure 3), it can be seen that the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is a target compound 2-1. The material has good thermal stability, and the decomposition temperature reaches above 510 ℃.
Compound 2-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 819.3785, test value: 820.5098. elemental analysis results: theoretical value: 87.90 percent of C; 5.66 percent of H; b, 1.32 percent; and 5.13 percent of N. Experimental values: 87.92 percent of C; 5.62 percent of H; b, 1.34 percent; and 5.14 percent of N. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 2-2. The material has good thermal stability, and the decomposition temperature reaches above 510 ℃.
Compounds 2-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 819.3785, test value: 820.5205. elemental analysis results: theoretical value: 87.90 percent of C; 5.66 percent of H; b, 1.32 percent; and 5.13 percent of N. Experimental values: 87.91 percent of C; 5.63 percent of H; b, 1.34 percent; and 5.13 percent of N. From the mass spectrum and the elemental analysis results and the single crystal structure analysis (figure 3), it can be known that the closed ring position of the B atom is on the fluorene group of the two fusion donors, and the product has a correct structure and is a target compound 2-3. The material has good thermal stability, and the decomposition temperature reaches above 510 ℃.
Synthetic example 3: the compounds 3-1 to 3-3 of the present invention can be synthesized by the following methods:
this example is substantially the same as synthetic example 1 except that: in this example, 4-bromofluorene needs to be replaced by the bromide at the 4-position of 9, 9-diphenylfluorene in equal amount, and the rest conditions are kept unchanged. Finally, bright yellow solid powder which is a mixture of three stereoisomers 3-1, 3-2 and 3-3, 8.3g and has a yield of 58.6% is obtained, then the three stereoisomers are further analyzed in a ratio of 3:6:1 by supercritical fluid chromatography, the spatial structures of the three isomers can be confirmed by single crystal analysis, as shown in the attached figure 3, different positions of B atoms and N atoms are indicated in the figure, and the structures of the three isomers can be judged by the closed ring position of the B atoms.
Compound 3-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 1067.4411, test value: 1068.1430. elemental analysis results: theoretical value: 89.96 percent of C; 5.10 percent of H; 1.01 percent of B; and 3.93 percent of N. Experimental values: 89.99 percent of C; 5.07 percent of H; 1.02 percent of B; n is 3.92 percent. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is a target compound 3-1. The material has good thermal stability, and the decomposition temperature reaches over 440 ℃.
Compound 3-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 1067.4411, test value: 1068.3526. elemental analysis results: theoretical value: 89.96 percent of C; 5.10 percent of H; 1.01 percent of B; and 3.93 percent of N. Experimental values: 89.98 percent of C; 5.08 percent of H; b, 1.03 percent; n is 3.92 percent. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 3-2. The material has good thermal stability, and the decomposition temperature reaches more than 460 ℃.
Compound 3-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 1067.4411, test value: 1068.5410. elemental analysis results: theoretical value: 89.96 percent of C; 5.10 percent of H; 1.01 percent of B; and 3.93 percent of N. Experimental values: 89.99 percent of C; 5.05 percent of H; b, 1.04 percent; and N is 3.91 percent. From the mass spectrum and the elemental analysis results and the single crystal structure analysis (figure 3), it can be known that the closed ring position of the B atom is on the fluorene group of the two fusion donors, and the product has a correct structure and is the target compound 3-3. The material has good thermal stability, and the decomposition temperature reaches over 530 ℃.
Synthetic example 4: the compounds 4-1 to 4-3 of the present invention can be synthesized by the following methods:
this example is substantially the same as synthetic example 1 except that: in this example, 4-bromofluorene needs to be replaced by the bromide at the 4-site of 9-fluorenone in equal amount, and the rest conditions are kept unchanged. Finally, bright yellow solid powder which is a mixture of three stereoisomers 4-1, 4-2 and 4-3, 5.8g and has a yield of 55.3% is obtained, then the three stereoisomers are further analyzed in a ratio of 2:7:1 by supercritical fluid chromatography, the spatial structures of the three isomers can be confirmed by single crystal analysis, as shown in figure 3, different positions of B atoms, O atoms and N atoms are indicated in the figure, and the structures of the three isomers can be judged by the closed-loop position of the B atoms.
Compound 4-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 791.2744, test value: 792.2778. elemental analysis results: theoretical value: 84.96 percent of C; 4.33 percent of H; b, 1.37 percent; 5.31 percent of N; 4.04 percent of O. Experimental values: 84.99 percent of C; 4.30 percent of H; b, 1.33 percent; 5.34 percent of N; 4.05 percent of O. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is a target compound 4-1. The material has good thermal stability, and the decomposition temperature reaches more than 400 ℃.
Compound 4-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 791.2744, test value: 792.4827. elemental analysis results: theoretical value: 84.96 percent of C; 4.33 percent of H; b, 1.37 percent; 5.31 percent of N; 4.04 percent of O. Experimental values: 84.97 percent of C; 4.31 percent of H; b, 1.36 percent; 5.32 percent of N; 4.06 percent of O. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 4-2. The material has good thermal stability, and the decomposition temperature reaches more than 430 ℃.
Compound 4-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 791.2744, test value: 792.4882. elemental analysis results: theoretical value: 84.96 percent of C; 4.33 percent of H; b, 1.37 percent; 5.31 percent of N; 4.04 percent of O. Experimental values: 84.98 percent of C; 4.32 percent of H; b, 1.36 percent; 5.33 percent of N; 4.02 percent of O. From the mass spectrum and the elemental analysis results and the single crystal structure analysis (figure 3), it can be known that the closed ring position of the B atom is on the fluorene group of the two fusion donors, and the product has a correct structure and is 4-3 of the target compound. The material has good thermal stability, and the decomposition temperature reaches more than 460 ℃.
Synthesis example 5: the compounds 5-1 to 5-3 of the present invention can be synthesized by the following methods:
this example is substantially the same as synthetic example 1 except that: in this example, 4-bromofluorene needs to be replaced by the same amount of bromide at position 4 of 9, 9' -spirobifluorene, and the rest conditions are kept unchanged. Finally, bright yellow solid powder which is a mixture of three stereoisomers 5-1, 5-2 and 5-3, 6.6g and has a yield of 46.8% is obtained, then the three stereoisomers are analyzed in a ratio of 2:7:1 through supercritical fluid chromatography, the spatial structures of the three isomers can be confirmed through single crystal analysis, as shown in the attached figure 3, different positions of B atoms and N atoms are indicated in the figure, and the structures of the three isomers can be judged through the closed loop position of the B atoms.
Compound 5-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 1063.4098, test value: 1064.4131. elemental analysis results: theoretical value: 90.30 percent of C; 4.74 percent of H; 1.02 percent of B; and 3.95 percent of N. Experimental values: 90.31 percent of C; 4.77 percent of H; 1.02 percent of B; n is 3.92 percent. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is a target compound 5-1. The material has good thermal stability, and the decomposition temperature reaches more than 470 ℃.
Compound 5-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 1063.4098, test value: 1064.4336. elemental analysis results: theoretical value: 90.30 percent of C; 4.74 percent of H; 1.02 percent of B; and 3.95 percent of N. Experimental values: 90.34 percent of C; 4.73 percent of H; 1.01 percent of B; and 3.93 percent of N. From the results of mass spectrometry and elemental analysis and single crystal structure analysis (fig. 3), it can be seen that the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 5-2. The material has good thermal stability, and the decomposition temperature reaches above 490 ℃.
Compound 5-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight is 1063.4098, test value: 1064.4872. elemental analysis results: theoretical value: 90.30 percent of C; 4.74 percent of H; 1.02 percent of B; and 3.95 percent of N. Experimental values: 90.32 percent of C; 4.72 percent of H; 1.01 percent of B; and 3.96 percent of N. From the mass spectrum and the elemental analysis results and the single crystal structure analysis (figure 3), it can be known that the closed ring position of the B atom is on the fluorene group of the two fusion donors, and the product has a correct structure and is a target compound 5-3. The material has good thermal stability, and the decomposition temperature reaches above 490 ℃.
Similarly, the monoboron derivatives of compounds 6-1, 6-2, 6-3 to 12-1, 12-2, 12-3 can be synthesized analogously.
The monoboron derivative based on the fluoreno-aniline fusion donor has a higher thermal decomposition temperature than conventional materials such as the MR-TADF compound PAB (decomposition temperature 375 ℃, organic electronics.2021,97:106275) previously reported by this subject group, as shown in fig. 4. The good thermal stability of the material is beneficial to improving the stability of the device.
The above-mentioned monoboron derivative of the fluorene and aniline fusion donor may be applied to an organic electroluminescent device, and for example, one of the monoboron derivatives of the fluorene and aniline fusion donor or a mixture of two or three monoboron derivatives having isomers may be used as a light-emitting guest material of a light-emitting layer in the organic electroluminescent device. Fig. 1 is a schematic diagram of an exemplary electroluminescent device structure. Fig. 2 is a schematic diagram of an energy transfer process of a three-component mixed system constructed by using a monoboron derivative of a fluorene-aniline fusion donor as a luminescent guest material, wherein the compound represented by the general formula a-1 has the minimum conjugation degree, the compound represented by the general formula a-3 has the maximum conjugation degree, and the compound represented by the general formula a-2 has the conjugation degree between the two, so that energy transfer from a low-conjugation short-wavelength compound to a high-conjugation long-wavelength compound can be realized. The organic electroluminescent device correspondingly obtained comprises a counter electrode, a transmission layer between the counter electrode and the counter electrode, a luminescent layer and an injection layer, wherein the luminescent layer contains the mono-boron derivative of the fluorene aniline fusion donor.
One of the monoboron derivatives of the fluorene oaniline fused donor or a mixture of two or three monoboron derivatives with isomers can be used as a guest luminescent material to be applied to an OLED electroluminescent device. Specific device fabrication procedures may include, for example: (1) substrate pretreatment, namely, carrying out ultrasonic cleaning on an ITO (indium tin oxide) glass substrate in an ITO cleaning agent, isopropanol, acetone, ethanol and deionized water for 30 minutes in sequence, drying the substrate for 2 hours at 120 ℃ in an oven after drying nitrogen. Before preparing the device, the ITO glass substrate is treated for 5 minutes by oxygen plasma surface treatment, then is conveyed into an organic vacuum chamber to be evaporated with organic functional layer materials, and after the completion, the ITO glass substrate is transferred to a metal vacuum chamber to be evaporated with metal electrodes in vacuum. In a specific preparation process, an optimal host material, exciton blocking layer material or injection transport layer material can be selected according to the self properties of one of the monoboron derivatives of the fluorene aniline fusion donor or the mixture of two or three monoboron derivatives with isomers, such as an emission peak position, the lowest singlet state and triplet state energy values; in addition, the film thickness of each functional layer and the doping concentration of the host and the guest are also optimized by the system.
The following device examples (each organic functional layer was optimized):
device example 1:
ITO/PEDOT：PSS(40nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(8wt％,25nm)/TSPO1(5nm)/TmPyPb(20nm)/LiF(1nm)/Al(140nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 1-1, 1-2 and 1-3 of the fluorene aniline fusion donor.
When the dose is 1-1 only, the peak wavelength of electroluminescence is 442nm, the full width at half maximum (FWHM) is 22nm, and the maximum External Quantum Efficiency (EQE) max ) 15.6%, device lifetime LT 95 Is 80 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 1-1 and 1-3 (1-1 and 1-3 in a ratio of 9: 1; mass ratio, the same applies hereinafter). The peak wavelength of electroluminescence is 490nm, FWHM is 28nm, EQE max 18.3%, device lifetime LT 95 Is 95 hours @ initial luminance 2000cd/m 2 。
When the dose is a mixture of 1-1, 1-2 and 1-3 (the ratio of 1-1 to 1-2 to 1-3 is 6: 3: 1), the electroluminescence peak wavelength is 490nm, the FWHM is 28nm, and the EQE is max 25.5%, device lifetime LT 95 Is 110 hours @ initial luminance 2000cd/m 2 。
Device example 2:
ITO/TAPC(50nm)/TCTA(30nm)/mCP(5nm)/mCP:Dopant(10wt％,30nm)/TmPyPb(30nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 2-1, 2-2 and 2-3 of the fluorene aniline fusion donor.
When the dose is only 2-1, the peak wavelength of electroluminescence is 449nm, the full width at half maximum (FWHM) is 21nm, and the maximum External Quantum Efficiency (EQE) max ) 15.4%, device lifetime LT 95 Is 74 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 2-1 and 2-2 (2-1 and 2-2 in a ratio of 20: 1). Electroluminescent peakThe value wavelength was 469nm, FWHM 25nm, EQE max 23.1%, device lifetime LT 95 Is 88 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 2-1, 2-2 and 2-3 (2-1 and 2-2 and 2-3 in a ratio of 10: 2: 1), the electroluminescence peak wavelength is 485nm, the FWHM is 27nm, and the EQE is max 27.1%, device lifetime LT 95 Is 105 hours @ initial luminance 2000cd/m 2 。
Device example 3:
ITO/NPD(60nm)/TCTA(20nm)/mCP(5nm)/mCBP:Dopant(5wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of monoboron derivatives 3-1, 3-2 and 3-3 of the fluorene dianiline fusion donor in the invention.
When the dose is only 3-1, the peak wavelength of electroluminescence is 455nm, the full Width at half maximum (FWHM) is 23nm, and the maximum External Quantum Efficiency (EQE) max ) 17.8%, device lifetime LT 95 Is 92 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 3-2 and 3-3 (the ratio of 3-2 to 3-3 is 10: 1). The peak wavelength of electroluminescence is 492nm, FWHM is 26nm, EQE max 29.3%, device lifetime LT 95 Is 98 hours @ initial luminance 2000cd/m 2 。
When the dose is a mixture of 3-1, 3-2 and 3-3 (the ratio of 3-1 to 3-2 to 3-3 is 6: 3: 1), the electroluminescence peak wavelength is 492nm, the FWHM is 27nm, and the EQE is max 34.8%, device lifetime LT 95 Is 118 hours @ initial luminance 2000cd/m 2 。
Device example 4:
ITO/HATCN(50nm)/TCTA(30nm)/mCP(5nm)/mCBP:Dopant(3wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 4-1, 4-2 and 4-3 of the fluorene aniline fusion donor.
When the dose is only 4-1, the peak wavelength of electroluminescence is 442nm, the full width at half maximum (FWHM) is 23nm, and the maximum External Quantum Efficiency (EQE) max ) 13.5%, device lifetime LT 95 Is 61 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 4-1 and 4-2 (4-1 and 4-2 in a 9: 1 ratio). The peak wavelength of electroluminescence is 460nm, FWHM is 27nm, EQE max 18.1%, device lifetime LT 95 Is 82 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 4-1, 4-2 and 4-3 (4-1 and 4-2 and 4-3 in a ratio of 20: 5: 1), the electroluminescence peak wavelength is 481nm, the FWHM is 29nm, and the EQE is max 26.5%, device lifetime LT 95 Is 92 hours @ initial luminance 2000cd/m 2 。
Device example 5:
ITO/NPD(60nm)/TCTA(20nm)/mCP(5nm)/mCBP:Dopant(6wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 5-1, 5-2 and 5-3 of the fluorene aniline fusion donor in the invention.
When the dose is only 5-1, the peak wavelength of electroluminescence is 458nm, the full width at half maximum (FWHM) is 20nm, and the maximum External Quantum Efficiency (EQE) max ) 19.1%, device lifetime LT 95 Is 94 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 5-1 and 5-2 (5-1 and 5-2 in a ratio of 10: 1). Peak wavelength of electroluminescence of 478nm, FWHM of 23nm, EQE max 23.9%, device lifetime LT 95 Is 104 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 5-1, 5-2 and 5-3 (5-1 and 5-2 and 5-3 in a ratio of 20: 5: 1), the electroluminescence peak wavelength is 494nm, the FWHM is 26nm, and the EQE is max 28.5%, device lifetime LT 95 Is 125 hours @ initial luminance 2000cd/m 2 。
Device example 6:
ITO/HAT-CN(15nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(1wt％,20nm)/PPF(6nm)/TmPyPb(20nm)/LiF(1nm)/Al(60nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 6-1, 6-2 and 6-3 of the fluorene dianiline fusion donor in the invention.
When the Dopant is only 6-1, the electroluminescence peak wavelength is 440nm, the full width at half maximum (FWHM) is 24nm, and the maximum External Quantum Efficiency (EQE) max ) 16.9%, device lifetime LT 95 Is 65 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 6-1 and 6-3 (6-1 and 6-3 in a 9: 1 ratio). The peak wavelength of electroluminescence is 484nm, FWHM is 26nm, EQE max 25.8%, device lifetime LT 95 Is 96 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 6-1, 6-2 and 6-3 (6-1 and 6-2 and 6-3 in a ratio of 6: 3: 1), the electroluminescence peak wavelength is 485nm, the FWHM is 27nm, and the EQE is max 30.1%, device lifetime LT 95 Is 102 hours @ initial luminance 2000cd/m 2 。
Device example 7:
ITO/HAT-CN(15nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(1wt％,20nm)/PPF(6nm)/TmPyPb(20nm)/LiF(1nm)/Al(60nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 7-1, 7-2 and 7-3 of the fluorene dianiline fusion donor in the invention.
When the dose is only 7-1, the peak wavelength of electroluminescence is 441nm, the full width at half maximum (FWHM) is 23nm, and the maximum External Quantum Efficiency (EQE) max ) 17.0%, device lifetime LT 95 Is 71 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 7-1 and 7-2 (7-1 and 7-2 in a ratio of 20: 1). The peak wavelength of electroluminescence is 464nm, FWHM is 25nm, EQE max 25.6%, device lifetime LT 95 Is 89 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 7-1, 7-2 and 7-3 (ratio of 7-1 to 7-2 to 7-3 is 20: 2: 1), the electroluminescence peak wavelength is 485nm, FWHM is 25nm, EQE max 28.2%, device lifetime LT 95 Is 106 hours @ initial luminance 2000cd/m 2 。
Device example 8:
ITO/NPD(30nm)/TCTA(20nm)/mCP(5nm)/mCBP:Dopant(3wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 8-1, 8-2 and 8-3 of the fluorene dianiline fusion donor in the invention.
When the dose is only 8-1, the peak wavelength of electroluminescence is 455nm, the full Width at half maximum (FWHM) is 23nm, and the maximum External Quantum Efficiency (EQE) max ) 17.6%, device lifetime LT 95 Is 82 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 8-2 and 8-3 (8-2 and 8-3 in a ratio of 10: 1). The peak wavelength of electroluminescence is 496nm, FWHM is 26nm, EQE max 27.9%, device lifetime LT 95 Is 99 hours @ initial luminance 2000cd/m 2 。
When the Dopantt is a mixture of 8-1, 8-2 and 8-3 (8-1 and 8-2 and 8-3 in a ratio of 6: 3: 1), the electroluminescence peak wavelength is 497nm, the FWHM is 27nm, and the EQE is max 29.5%, device lifetime LT 95 Is 121 hours @ initial luminance 2000cd/m 2 。
Device example 9:
ITO/NPB(30nm)/TCTA(15nm)/mCP(5nm)/mCBP:Dopant(5wt％,25nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (dot) is one or two or three of the monoboron derivatives 9-1, 9-2 and 9-3 of the fluorene aniline fusion donor in the invention.
When the dose is only 9-1, the peak wavelength of electroluminescence is 456nm, the full Width at half maximum (FWHM) is 23nm, and the maximum External Quantum Efficiency (EQE) max ) 18.1%, device lifetime LT 95 Is 83 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 9-1 and 9-2 (9-1 and 9-2 in a ratio of 10: 1). Peak wavelength of electroluminescence of 476nm, FWHM of 25nm, EQE max 27.6%, device lifetime LT 95 Is 88 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 9-1, 9-2 and 9-3 (the ratio of 9-1 and 9-2 and 9-3 is 20: 3: 1), the electric field is generatedThe peak wavelength of luminescence is 498nm, FWHM is 26nm, EQE max 32.7%, device lifetime LT 95 Is 122 hours @ initial luminance 2000cd/m 2 。
Device example 10:
ITO/TAPC(60nm)/TCTA(5nm)/mCP(5nm)/mCBP:Dopant(5wt％,20nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 10-1, 10-2 and 10-3 of the fluorene dianiline fusion donor in the invention.
When the dose is only 10-1, the peak wavelength of electroluminescence is 458nm, the full width at half maximum (FWHM) is 20nm, and the maximum External Quantum Efficiency (EQE) max ) 16.2%, device lifetime LT 95 Is 91 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 10-1 and 10-2 (10-1 and 10-2 in a ratio of 20: 1). The peak wavelength of electroluminescence is 480nm, FWHM is 23nm, EQE max 24.8%, device lifetime LT 95 Is 102 hours @ initial luminance 2000cd/m 2 。
When the dose is a mixture of 10-1, 10-2 and 10-3 (ratio of 10-1 to 10-2 to 10-3 is 20: 3: 1), the electroluminescence peak wavelength is 499nm, the FWHM is 26nm, and the EQE is max 34.7%, device lifetime LT 95 Is 123 hours @ initial luminance 2000cd/m 2 。
Device example 11:
ITO/HAT-CN(10nm)/TAPC(30nm)/TCTA(15nm)/mCP(5nm)/mCP:Dopant(1wt％,20nm)/PPF(6nm)/TPBi(20nm)/LiF(1nm)/Al(100nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of monoboron derivatives 11-1, 11-2 and 11-3 of the fluorene dianiline fusion donor in the invention.
When the dose is only 11-1, the peak wavelength of electroluminescence is 452nm, the full width at half maximum (FWHM) is 23nm, and the maximum External Quantum Efficiency (EQE) max ) 16.6%, device lifetime LT 95 Is 66 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 11-1 and 11-3 (11-1 and 11-3 in a ratio of 10: 1). Electroluminescence (EL)Peak wavelength 493nm, FWHM 26nm, EQE max 24.9%, device lifetime LT 95 Is 93 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 11-1, 11-2 and 11-3 (the ratio of 11-1 to 11-2 to 11-3 is 20: 5: 1), the electroluminescence peak wavelength is 493nm, the FWHM is 26nm, and the EQE is max 29.5%, device lifetime LT 95 Is 104 hours @ initial luminance 2000cd/m 2 。
Device example 12:
ITO/HAT-CN(15nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(3wt％,20nm)/DPEPO(5nm)/TmPyPb(20nm)/LiF(1nm)/Al(60nm).
the luminescent layer guest luminescent material (Dopant) is one or two or three of the monoboron derivatives 12-1, 12-2 and 12-3 of the fluorene dianiline fusion donor in the invention.
When the dose is only 12-1, the peak wavelength of electroluminescence is 450nm, the full width at half maximum (FWHM) is 21nm, and the maximum External Quantum Efficiency (EQE) max ) 17.5%, device lifetime LT 95 Is 73 hours @ initial luminance 2000cd/m 2 。
When the Dopan is a mixture of 12-1 and 12-2 (12-1 and 12-2 in a ratio of 20: 1). Peak wavelength of electroluminescence is 471nm, FWHM is 23nm, EQE max 26.0%, device lifetime LT 95 Is 89 hours @ initial luminance 2000cd/m 2 。
When the Dopant is a mixture of 12-1, 12-2 and 12-3 (the ratio of 12-1 to 12-2 to 12-3 is 20: 5: 1), the electroluminescence peak wavelength is 490nm, the FWHM is 25nm, and the EQE is max 33.6%, device lifetime LT 95 Is 107 hours @ initial luminance 2000cd/m 2 。
The above examples demonstrate that the monoboron derivative based on the fluorene aniline fusion donor of the present invention has very narrow half-peak width, and can effectively improve the color purity of the device. By optimizing the device preparation process, the OLED device of the single fluorene aniline fusion donor monoboron derivative or the two or three component self-sensitized OLED device with the isomer can obtain higher device efficiency, and the external quantum efficiency (EQE is more than 20%) of the two or three component self-sensitized device with the isomer can be improved by more than 50% compared with the single component device efficiency.
FIG. 5 is a graph showing the external quantum efficiency versus current density characteristic of three-component self-sensitized devices in device examples 1 to 5. A clear conclusion can be drawn from the external quantum efficiency curve of the three-component self-sensitized device, and the luminous efficiency of the material is at a higher level, thereby meeting the requirements of the industrialized application of the organic electroluminescent material.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A monoboron derivative based on a fluorene oaniline fusion donor, characterized in that the monoboron derivative has a general structure as shown in at least one of general formula A-1 to general formula A-3:
wherein the R group is selected from: a fluorene group or a fluorene derivative group having 13 to 38 carbon atoms;
and, for formulas A-2 and A-3, the R group is bonded to the boron atom in the formula, the bonding atom is the carbon atom at position 3 of the R group, and the nitrogen atom is bonded to the carbon atom at position 4 of the R group.
2. The monoboron derivative of claim 1, wherein the monoboron derivative is prepared from an intermediate having a general structure as shown in formula a, and the target product is three stereoisomeric monoboron derivatives having general structures as shown in formulae a-1 to a-3;
3. the monoboron derivative of claim 1 wherein the R group is fluorenyl;
or the R group is 9, 9-dimethylfluorenyl;
or the R group is 9, 9-diphenylfluorenyl;
or, the R group is 9-fluorenone;
or, the R group is 9, 9' -spirobifluorenyl;
or, the R group is dibenzofuranyl;
or, the R group is dibenzothienyl;
or the R group is spiro [ fluorene-9, 9' -xanthene ] group;
or the R group is spiro [ fluorene-9, 9' -thiaanthracene ] group;
or the R group is 10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] group;
or the R group is 10, 10-dimethyl-10H-spiro [ anthracene-9, 9' -fluorene ] group;
or the R group is 10, 10-diphenyl-10H-spiro [ anthracene-9, 9' -fluorene ] group.
4. A process for the preparation of monoboron derivatives based on fluorene oaniline fusion donors according to any one of claims 1 to 3 comprising the steps of:
(1) 1,3, 5-trihalo substituted benzene is used as a raw material and is matched with a raw material diphenylamine to carry out Buchwald-Hartwig reaction to obtain a 3, 5-dihalo triphenylamine compound;
(2) taking a halide R-X corresponding to the R group as a raw material, matching with aniline as a raw material, and carrying out a C-N coupling reaction on the halide R-X and the aniline through palladium catalysis to obtain a fluorene aniline fusion donor containing the R group; wherein, for the halide corresponding to the R group, the halogen X is positioned at the No. 4 site of the R group; the halogen X is fluorine, chlorine, bromine or iodine;
(3) taking the 3, 5-dihalogen triphenylamine compound obtained in the step (1) and the fluorene group-containing aniline fusion donor obtained in the step (2) as raw materials, and carrying out C-N coupling reaction on the raw materials under the catalysis of palladium to obtain an intermediate shown in a general formula A;
(4) using halogen substituent BX of boron for the intermediate obtained in the step (3) 3 (ii) undergoing a borohybrid-Krafft Reaction (Tandem Bora-Friedel-Crafts Reaction) to yield a monoboron derivative based on a fluorene-based acene amine fusion donor; wherein, the halogen substituent BX of the boron 3 In particular to boron trichloride BCl 3 Boron tribromide BBr 3 Or boron triiodide BI 3 。
5. The method according to claim 4, wherein in the step (1), the C-N coupling reaction is carried out in a solvent system under the participation of a ligand and alkali, and specifically comprises the following steps of mixing 1,3, 5-trihalo-substituted benzene raw material, diphenylamine raw material, palladium catalyst, ligand, alkali and solvent according to the volume ratio of the 1,3, 5-trihalo-substituted benzene raw material, diphenylamine raw material, palladium catalyst, ligand and alkali to the solvent of 1mmol:1mmol:0.01-0.03mmol:0.03-0.05mmol:3-5mmol:5 to 10ml of the mixture is added into a reaction device, then blowing out air by using nitrogen, heating to a reflux state under the protection of nitrogen, reacting for 8-48 hours, cooling to room temperature after complete reaction, and carrying out purification post-treatment to obtain a 3, 5-dihalogen triphenylamine compound;
wherein, the halogens at the 1 position, the 3 position and the 5 position in the 1,3, 5-trihalo-substituted benzene are selected from fluorine, chlorine, bromine and iodine, and the reaction activity of the halogen at the 1 position is higher than that at the 3 position and the 5 position; the ligand is a phosphine-containing ligand, preferably tri-tert-butylphosphine tetrafluoroborate (t-Bu) 3 PHBF 4 ) (ii) a The base is an organic base, preferably sodium tert-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is preferably tris-dibenzylidene acetone dipalladium;
in the step (2), the C-N coupling reaction is carried out in a solvent system under the participation of a ligand and an alkali, specifically, a halide raw material, an aniline raw material, a palladium catalyst, a ligand, an alkali and a solvent corresponding to the R group are added into a reaction device according to the volume ratio of the halide raw material, the aniline raw material, the palladium catalyst, the ligand and the alkali to the solvent of 1mmol:1-2mmol:0.01-0.03mmol:0.03-0.05mmol:3-5mmol:5-10ml, then air is blown off by using nitrogen, then the reaction is heated to a reflux state under the protection of nitrogen for 8-48 hours, and after the reaction is completed, the reaction is cooled to room temperature for purification and post-treatment, so that a fluorene and aniline fusion donor containing the R group can be obtained;
wherein the ligand is a phosphine-containing ligand, preferably tri-tert-butylphosphine tetrafluoroborate (t-Bu) 3 PHBF 4 ) (ii) a The base is an organic base, preferably sodium tert-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is preferably tris-dibenzylideneacetone dipalladium.
6. The preparation method according to claim 4, wherein in the step (3), the C-N coupling reaction is carried out in a solvent system in the presence of a ligand and a base, and specifically, the 3, 5-dihalogenated triphenylamine compound raw material, the R group-containing fluorenes-and-anilines fusion donor raw material, the palladium catalyst, the ligand, the base and the solvent are added into a reaction device in such an amount that the volume ratio of the 3, 5-dihalogenated triphenylamine compound raw material, the R group-containing fluorenes-and-anilines fusion donor raw material, the palladium catalyst, the ligand and the base is 1mmol:2-2.5mmol:0.02-0.05mmol:0.05-0.10mmol:3-6mmol:6-15ml, air is blown off by using nitrogen gas, then the reaction is heated to a reflux state under the protection of nitrogen gas for 12-60 hours, after the reaction is completed, the reaction is cooled to room temperature for purification treatment, obtaining an intermediate shown as a general formula A;
wherein the ligand is a phosphine-containing ligand, preferably 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (SPhos); the base is an organic base, preferably sodium tert-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is palladium acetate (Pd (OAc) 2 )。
7. The preparation method according to claim 4, wherein the step (4) is specifically: vacuum drying the intermediate at 80-120 deg.C for 8-24 hr before reaction, dissolving the intermediate in o-dichlorobenzene (o-DCB) solvent, ultrasonic treating to dissolve completely, blowing off nitrogen, stirring at room temperature under nitrogen protection, and slowly adding BX dropwise at a temperature lower than room temperature 3 Is droppedAfter the addition is finished, heating the reaction system to 150-250 ℃, and stirring for reaction for 20-48 hours; then, cooling to room temperature, putting the system into an ice bath, keeping the temperature below 0 ℃, adding N.N-Diisopropylethylamine (DIPEA), reacting for 1-5 hours, carrying out reduced pressure distillation to remove the solvent, and then carrying out column chromatography separation and purification to obtain the monoboron derivative with the general structure shown in the general formula A-1 to the general formula A-3;
wherein the amount of substance of the intermediate, the volume of the ortho-dichlorobenzene, the BX 3 The ratio of the amount of said substance of N.N-Diisopropylethylamine (DIPEA) to the amount of said substance of N.N-Diisopropylethylamine (DIPEA) satisfies 1mmol:10-30ml:1.5-24mmol:12-18 mmol.
8. Use of the mono-boron derivative based on a fluorene-based oaniline-fusion donor according to any one of claims 1-3 in the light emitting layer of an organic electroluminescent device;
preferably, the organic electroluminescent device comprises in sequence: the light-emitting diode comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode;
more preferably, an exciton blocking layer is further disposed between the hole transport layer and the light emitting layer; an exciton blocking layer is also disposed between the light emitting layer and the electron transport layer.
9. Use according to claim 8, wherein the monoboron derivative based on a fluorene-based and aniline fusion donor is used in particular as guest light-emitting material in the light-emitting layer of an organic electroluminescent device.
10. The use of claim 8, wherein the monoboron derivative has a general structure shown by two or three of formulas a-1 to a-3.
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