CN116925113A - Boron nitrogen heterocyclic compound, composition containing same and application thereof - Google Patents
Boron nitrogen heterocyclic compound, composition containing same and application thereof Download PDFInfo
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- CN116925113A CN116925113A CN202210351945.2A CN202210351945A CN116925113A CN 116925113 A CN116925113 A CN 116925113A CN 202210351945 A CN202210351945 A CN 202210351945A CN 116925113 A CN116925113 A CN 116925113A
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- substituted
- aryl
- independently
- alkyl
- membered heteroaryl
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- -1 Boron nitrogen heterocyclic compound Chemical class 0.000 title claims abstract description 93
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 85
- 125000003118 aryl group Chemical group 0.000 claims description 94
- 125000000217 alkyl group Chemical group 0.000 claims description 71
- 125000001072 heteroaryl group Chemical group 0.000 claims description 63
- 229910052805 deuterium Inorganic materials 0.000 claims description 39
- 125000003545 alkoxy group Chemical group 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 31
- 238000002347 injection Methods 0.000 claims description 29
- 239000007924 injection Substances 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052731 fluorine Inorganic materials 0.000 claims description 27
- 239000011737 fluorine Substances 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 230000005525 hole transport Effects 0.000 claims description 16
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 229910052582 BN Inorganic materials 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 7
- 125000002950 monocyclic group Chemical group 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 4
- 125000003003 spiro group Chemical group 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims description 2
- 150000003230 pyrimidines Chemical class 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 125000004306 triazinyl group Chemical group 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 claims 1
- 238000001228 spectrum Methods 0.000 abstract description 20
- 239000010410 layer Substances 0.000 description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229920000144 PEDOT:PSS Polymers 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001748 luminescence spectrum Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000004382 visual function Effects 0.000 description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- 235000009161 Espostoa lanata Nutrition 0.000 description 2
- 240000001624 Espostoa lanata Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 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
- 230000007547 defect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001786 isothiazolyl group Chemical group 0.000 description 2
- 125000000842 isoxazolyl group Chemical group 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 125000002098 pyridazinyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000335 thiazolyl group Chemical group 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical group C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004857 imidazopyridinyl group Chemical group N1C(=NC2=C1C=CC=N2)* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229940037201 oris Drugs 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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Abstract
The invention discloses a boron nitrogen heterocyclic compound, a composition containing the boron nitrogen heterocyclic compound and application of the boron nitrogen heterocyclic compound. The boron nitrogen heterocyclic compound has a structure shown in a formula I, adopts a binuclear strategy to realize effective red shift of BN derivative spectrum, has a narrow spectrum, is used as a narrow spectrum luminescent material for preparing a luminescent layer of an organic electroluminescent device, and the prepared organic electroluminescent device realizes narrow spectrum TADF emission, and ensures that the electroluminescent external quantum efficiency of the device is up to more than 38.5 percent.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescence, and particularly relates to a boron-nitrogen heterocyclic compound, a composition containing the same and application thereof.
Background
The organic photoelectric material (Organic Optoelectronic Materials) is an organic material having the characteristics of generation, conversion, transmission and the like of photons and electrons. Currently, the controllable photoelectric property of Organic photoelectric materials has been applied to Organic Light-Emitting diodes (OLED), organic solar cells (OPV: organic Photovoltage), organic field effect transistors (OFET: organic Field Effect Transistor), and even Organic lasers. In recent years, OLEDs have become a very popular new flat display product at home and abroad. The OLED display has the characteristics of self-luminescence, wide viewing angle, short reaction time, high luminous efficiency, wide color gamut, low working voltage, thin panel, capability of manufacturing a large-size flexible panel and low cost, and is known as a star flat display product in the 21 st century.
The history of organic electroluminescence can be traced back to the report of Bernanose et al in 1953 (see Papkovski D.B.Sens. And achuotors B.,1995,29,213.). After about 10 years, as compared with 1963, pope et al, new York university, applied a voltage across the crystals of anthracene, fluorescence emission of anthracene could be observed. (see M.Pope, H.Kallmann and P.Magnante, J.Chem.Phys.,1963,38,2042). In 1987, C.W.Tang et al, kodak, U.S. used an ultrathin film technique to prepare a light-emitting device with an aromatic amine having a good hole transport effect as a hole transport layer, an aluminum complex of 8-hydroxyquinoline as a light-emitting layer, and an Indium Tin Oxide (ITO) film and a metal alloy as an anode and a cathode, respectively. The device obtains brightness of up to 1000cd/m under 10V driving voltage 2 Is 1.5lm/W (see C.W.Tang and S.A.VanSlyke, appl.Phys.Lett.,1987, 51, 913). This breakthrough progress has led to rapid and intensive research into organic electroluminescence worldwide. In 1990, burroughes et al, university of Cambridge, proposed the first polymer (PPV) based light emitting diode. PPV has been shown to be highly fluorescent as an emissive material in a single layer device with high luminous efficiency (see burrouges j.h., bradley d.d. c., brown a.r., marks r.n., mackay k., friend R.H, burns p.l., holmes a.b., nature,1990,347,539.). Baldo, forrest et al, university of Princeton 1998, reported the first electroluminescent-based phosphorescent device, which in principle can have an internal quantum yield of 100%. (see M.A.Baldo, D.F.O' Briiental, nature,1998, 395, 151.) however, on the one hand, noble metals such as iridium platinum are commonly used as phosphorescent materials, and on the other hand, chemical instability still exists for deep blue phosphorescent materials, and the problem that the efficiency of the device drops greatly under high current density is solved, so that it is very important to develop an OLED device which uses cheap and stable organic small molecular materials and can realize high-efficiency luminescence.
In 2012, the Adachi research group at university of ninety reported a highly efficient fully fluorescent OLED device based on a Thermally Activated Delayed Fluorescence (TADF) mechanism. (Uoyama H, goushi K, shizu K, et al Highly efficient organic light-emitting diodes from delayed fluorescence [ J ]. Nature,2012,492 (7428):234-238.) when the S1 and T1 energy levels of the molecule are sufficiently small, triplet excitons can absorb thermal energy, return to singlet state through RISC process, and emit fluorescence, the Internal Quantum Efficiency (IQE) of the device can reach 100% in theory, and the External Quantum Efficiency (EQE) is even as high as 30% compared to the level of shoulder phosphorescence device. As a next-generation light-emitting material, a TADF material is being studied.
The TADF molecules are primarily doped as guest materials in a wide bandgap host material to achieve high efficiency thermally activated delayed fluorescence (see Q.Zhang, J.Li, K.Shizu, S.Huang, S.Hirata, H.Miyazaki, C.Adachi, J.Am.Chem.Soc.2012,134,14706; H.Uoyama, K.Goushi, K.Shizu, H.Nomura, C.Adachi, nature,2012,492, 234; t. Nishimoto, t. Yasuda, s.y. Lee, r. Kondo, c. Adachi, mater. Horiz.,2014,1,264). Unlike traditional fluorescent molecular Localized (LE) state luminescence, TADF emission is mainly derived from transitions in ICT state, and is therefore susceptible to interdonor-acceptor vibration and rotational movement, resulting in a broader spectrum. The broad spectrum, while advantageous for illumination applications, does not meet the high color purity requirements of the display field. While the most important use of OLEDs is in display, narrow spectral designs (i.e., smaller full width at half maximum, FWHM) of TADF materials are necessary. Recently, the boron-nitrogen resonance heterocycle based luminescent compound shows the characteristic of narrow band luminescence (Adv.Mater.2016, 28,2777;Nat.Photonics 2019,13,678;Angew.Chem.Int.Ed.2019,58,16912;Angew.Chem.Int.Ed.2020,59,17442), and the organic electroluminescent device prepared from the material has the advantage of high color purity. However, the kinds and the amounts of such luminescent materials are limited by the synthetic methods and purification of such materials, which limits the applications thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a boron-nitrogen heterocyclic luminescent compound and application thereof, and the compound provided by the invention aims to solve the defect of few types of TADF luminescent molecules, provide a narrow-spectrum luminescent material and regulate and control the emission wavelength of an emission spectrum by constructing derivatives with different substituents. The synthesis method of the boron-nitrogen heterocyclic luminescent compound, the luminescent material and the application of the luminescent material as the narrow spectrum luminescent material in preparing the luminescent layer of the organic electroluminescent device, and the prepared organic electroluminescent device realizes narrow spectrum TADF emission.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a boron nitrogen heterocyclic compound shown as a formula I,
wherein, -E-represents a C-C single bond, i.e. the R group is linked to the benzene ring by a C-C single bond;
r is independently C 6 ～C 30 Aryl, 5-36 membered heteroaryl, substituted with one or more R m1 Substitution C 6 ～C 30 Aryl, or substituted by one or more R m1 Substituted 5-36 membered heteroaryl;
R m1 each occurrence is independently H, D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, substituted by one or more R m2 Substituted C 1 ～C 20 Alkyl, C 3 ～C 12 Cycloalkyl, C 1 ～C 12 Alkoxy, C 6 ～C 18 Aryl, 5-30 membered heteroaryl, diphenylamino, substituted with one or more R m2 Substitution C 6 ～C 18 Aryl, substituted by one or more R m2 Substituted with 5-to 30-membered heteroaryl, or with one or more R m2 Substituted diphenylamino groups;
R m2 each occurrence is independently H, D (deuterium), fluorine, CN, biphenyl, C 1 ～C 12 Alkyl, C 6 ～C 18 Aryl substituted C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 6 ～C 18 Aryl or 5-18 membered heteroaryl;
R 1 and R is 2 H, D (deuterium), fluorine, CN, C independently 1 ～C 20 Alkyl, substituted by one or more R a Substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Alkoxy, C 3 ～C 12 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R a Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R a Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R a Substituted diphenylamino groups;
R a each occurrence is independently D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, substituted by one or more R b Substituted C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 12 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R b Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R b Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R b Substituted diphenylamino groups;
R b each occurrence is independently D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R c Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R c Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R c Substituted diphenylamino groups;
R c each occurrence is independently D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R d Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R d Substituted 5-18 membered heteroaryl, diphenylamino, orIs/are R d Substituted diphenylamino groups;
R d each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 6 ～C 18 Aryl or by one or more R e Substituted C 6 ～C 18 An aryl group;
R e each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy or C 6 ～C 14 An aryl group;
the aryl and heteroaryl are independently monocyclic, fused or spiro;
the number of heteroatoms in the heteroaryl is independently 1, 2 or 3, and each heteroatom is independently N, O or S.
In one embodiment, the R 1 And R is 2 H, D (deuterium), fluorine, C 1 ～C 12 Alkyl, C substituted by one or more phenyl groups 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, phenyl, substituted with at least one C 1 ～C 12 Aryl substituted by alkyl, substituted by at least one C 1 ～C 12 Alkoxy-substituted aryl, diphenylamino, substituted by at least one C 1 ～C 12 Alkyl-substituted diphenylamino, carbazolyl, substituted by at least one C 1 ～C 12 Alkyl-substituted carbazolyl.
In one embodiment, the R a Each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C substituted by one or more phenyl groups 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, at least one C 1 ～C 12 Phenyl substituted by alkyl, substituted by at least one C 1 ～C 12 Alkoxy-substituted phenyl, diphenylamino, substituted by at least one C 1 ～C 12 Alkyl-substituted diphenylamino, carbazolyl, substituted by at least one C 1 ～C 12 Alkyl-substituted carbazolyl.
In one embodiment, the R b Each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, at least one C 1 ～C 12 Phenyl substituted by alkyl, substituted by at least one C 1 -C 12 Alkoxy-substituted phenyl, diphenylamino, substituted by at least one C 1 ～C 12 Alkyl-substituted diphenylamino, carbazolyl, substituted by at least one C 1 ～C 12 Alkyl-substituted carbazolyl.
In one embodiment, the R c Each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, at least one C 1 ～C 12 Phenyl substituted by alkyl, substituted by at least one C 1 ～C 12 Alkoxy-substituted phenyl, diphenylamino, substituted by at least one C 1 ～C 12 Alkyl-substituted diphenylamino, carbazolyl, substituted by at least one C 1 -C 12 Alkyl-substituted carbazolyl.
In one embodiment, the R d Each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, at least one C 1 ～C 12 Phenyl substituted by alkyl, substituted by at least one C 1 ～C 12 Alkoxy-substituted phenyl, diphenylamino, substituted by at least one C 1 ～C 12 Alkyl-substituted diphenylamino, carbazolyl, substituted by at least one C 1 ～C 12 Alkyl-substituted carbazolyl.
In one embodiment, the R 1 And R is 2 H, D (deuterium), fluorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, hexyl, octyl, decyl,Methoxy, ethyleneOxy, butoxy, hexyloxy,Cyclohexyl, adamantyl, phenyl, 4-methyl-phenyl, 4-ethyl-phenyl, 4-propyl-phenyl, 4-isopropylphenyl, 4-n-butylphenyl,/->
In some preferred embodiments, the R 1 And R is 2 H, C independently 1 ～C 20 Alkyl, substituted by one or more R a Substituted C 1 ～C 20 Alkyl, C 6 ～C 18 Aryl, substituted by one or more R a Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R a Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R a Substituted diphenylamino groups.
In some preferred embodiments, the R 1 And R is 2 In the definition of (C), said C 1 ～C 20 Alkyl is independently at each occurrence C 1 ～C 12 Alkyl radicals, e.g. methyl or
In some preferred embodiments, the R 1 And R is 2 In the definition of (C), said C 6 ～C 18 Aryl is independently phenyl at each occurrence.
In some preferred embodiments, the R 1 And R is 2 In the definition of (2), the 5-18 membered heteroaryl is independently at each occurrence a 5-13 membered heteroaryl, wherein the number of heteroatoms is 1 and the heteroatoms are N; for example, carbazolyl
In some preferred embodiments, the R a Independently at each occurrence C 1 ～C 12 Alkyl, substituted by one or more R b Substituted C 1 ～C 12 Alkyl or C 6 ～C 18 Aryl groups.
In some preferred embodiments, the R a In the definition of (C), said C 1 ～C 12 Alkyl is independently methyl, isopropyl or tert-butyl at each occurrence.
In some preferred embodiments, the R a In the definition of (C), said C 6 ～C 18 Aryl is independently phenyl at each occurrence.
In some preferred embodiments, the R b Independently at each occurrence C 6 ～C 18 Aryl groups.
In some preferred embodiments, the R b In the definition of (C), said C 6 ～C 18 Aryl is independently phenyl at each occurrence.
In some preferred embodiments, the R a Is H, methyl, isopropyl, tert-butyl or
In some preferred embodiments, the R 1 And R is 2 Independently H, methyl,Phenyl group,/->
In some preferred embodiments, the R 1 And R is 2 The same applies.
In some preferred embodiments, the R 1 And R is 2 Independently H, methyl,Phenyl group,/-> R g Independently H or R a . More preferably, R g Independently H, methyl, isopropyl, tert-butyl or +.>
In some preferred embodiments, the R 1 And R is 2 The same is H, methyl,Phenyl group,/-> R g Independently H or R a . More preferably, R g Independently H, methyl, isopropyl, tert-butyl or +.>
In one embodiment, R m1 Each occurrence is independently CN, C 6 ～C 18 Aryl, 5-30 membered heteroaryl, diphenylamino, substituted with one or more R m2 Substitution C 6 ～C 18 Aryl, substituted by one or more R m2 Substituted with 5-to 30-membered heteroaryl, or with one or more R m2 Substituted diphenylamino groups.
In one placeIn one embodiment, R m2 At each occurrence independently is biphenyl, C 1 ～C 12 Alkyl, C 6 ～C 18 Aryl substituted C 1 ～C 12 Alkyl or C 6 ～C 18 Aryl groups.
In one embodiment, in the definition of R, the C 6 ～C 30 Aryl is independently at each occurrence C 6 ～C 25 An aryl group; for example phenyl or spirobifluorenyl
In one embodiment, in the definition of R, the 5-36 membered heteroaryl is independently at each occurrence a 5-26 membered heteroaryl, wherein the number of heteroatoms is 1 and the heteroatoms are N or O; for example, carbazolyl Or spirofluorenyloxyanthracenyl->
In one embodiment, the R m1 In the definition of (C), said C 6 ～C 18 Aryl is independently at each occurrence C 6 ～C 13 An aryl group; such as phenyl or fluorenyl.
In one embodiment, the R m1 In the definition of (2), the 5-30 membered heteroaryl is independently at each occurrence a 5-26 membered heteroaryl; for example pyrimidinylTriazinyl->Carbazolyl->5H-pyridoindolyl +.>9, 10-dihydroacridinyl->Phenothiazinyl groupPhenoxazinyl->Or spirofluorene azaanthryl->
In one embodiment, the R m2 In the definition of (C), said C 6 ～C 18 Aryl is independently phenyl at each occurrence.
In one embodiment, the R m2 In the definition of (C), said C 1 ～C 12 Alkyl is independently at each occurrence isopropyl or tert-butyl.
In one embodiment, R is any one of the structures R-n (n=1-18):
R 3 h, D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 6 ～C 18 Aryl, substituted by one or more R f Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R f Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R f Substituted diphenylamino groups;
R f each occurrence is independently D (deuterium), fluorine, CN、C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 6 ～C 14 Aryl or 5-18 membered heteroaryl;
R 4 H, D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 -C 10 Cycloalkyl, C 6 ～C 14 Aryl, covered by one or more g h Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R h Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R h Substituted diphenylamino groups;
R h each occurrence is independently D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 12 Cycloalkyl, C 6 ～C 14 Aryl or 5-18 membered heteroaryl;
R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 and R is 12 And R is 13 Independently D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy or C 6 ～C 14 Aryl groups.
In one embodiment, R is any one of the structures R-rm (m=1-26):
in one embodiment of the present disclosure, the compound of formula I is any one of the following compounds:
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in another aspect, the present invention provides a method for preparing the boron nitrogen heterocyclic compound shown in formula I, which comprises the following steps: carrying out the following Suzuki reaction on a compound shown in a formula II and a compound shown in a formula III to obtain the boron nitrogen heterocyclic compound shown in the formula I;
wherein Hal is halogen (e.g. Br) and the remaining groups are as defined above.
The conditions and operation of the Suzuki reaction may be those conventional in the art for such reactions, the following conditions being particularly preferred in the present invention:
The alkaline reagent of the Suzuki reaction is, for example, potassium phosphate.
The catalyst of the Suzuki reaction is Pd, for example 2 (dba) 3 。
The solvent for the Suzuki reaction is, for example, toluene.
In another aspect, the present invention provides an organic electroluminescent composition comprising a dopant material and a host material, the dopant material comprising the boron-nitrogen heterocyclic compound as described above in formula I.
In one embodiment of the present invention, the organic electroluminescent composition contains the doping material in an amount of 0.3 to 30.0wt% (e.g., 3 wt%) and the host material in an amount of 99.7 to 70.0wt% (e.g., 97%) by weight, based on the weight of the organic electroluminescent composition.
In one embodiment of the invention, the host material is a material having electron transport capability and/or hole transport capability and having a triplet energy that is higher than or near the triplet energy of the dopant material.
In a certain embodiment of the invention, the host material comprises a material a comprising a carbazole derivative and/or a carboline derivative and/or a material B comprising a pyrimidine derivative and/or a triazine derivative.
In one embodiment of the present invention, the host material comprises a material a and a material B in a weight ratio of 1:5 to 5:1, for example 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1.
In one embodiment of the invention, the host material, material A, comprises one or more of the compounds of the formula H-1, H-2, H-3, H-4, H-5, H-6 or H-7 (e.g., two, in a weight ratio of 1:5 to 5:1, e.g., 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1),
wherein X is 1 、Y 1 And Z 1 Is CH or N, and X 1 、Y 1 And Z 1 At most one of them is N;
R 1H and R is 2H Independently is any one of the following structures:
wherein X is 2 、Y 2 And Z 2 Is CH or N, and X 2 、Y 2 And Z 2 At most one of them is N;
R aH and R is bH H, C independently 1 ～C 20 Alkyl, C 1 ～C 20 Alkoxy group、C 6 ～C 20 Aryl, C 1 ～C 20 Alkyl substituted C 6 ～C 20 Aryl or C 1 ～C 20 Alkoxy substituted C 6 ～C 20 Aryl groups.
In one embodiment of the invention, the host material, material a, comprises one or more of the following compounds:
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in one embodiment of the invention, the host material, material B, comprises one or more of the compounds of the formula Trz1-A, trz2-A, trz-A, trz4-A, trz5-A or Trz6-A (e.g., two, in a weight ratio of 1:5 to 5:1, such as 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1),
Wherein R is 1a 、R 1b 、R 2a 、R 2b 、R 3a And R is 3b Wherein 1 or 2 are independently R Tz The remainder are independently hydrogen, deuterium, C 1 ～C 8 Alkyl, C 1 ～C 8 Alkoxy, C 6 ～C 18 Aryl, C 1 ～C 8 Alkyl substituted C 6 ～C 18 Aryl or C 1 ～C 8 Alkoxy substituted C 6 ～C 18 Aryl of (a);
R Tz independently any of the groups shown below:
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wherein asterisks indicate the attachment site of the group.
In one embodiment of the present invention, the host material, material B, comprises one or more of the following compounds:
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in another aspect, the present invention provides an application of the boron nitrogen heterocyclic compound shown in formula I or the organic electroluminescent composition as an organic electroluminescent material.
In a preferred embodiment of the present invention, the boron nitrogen heterocyclic compound shown in formula I can be used as a doped luminescent material.
In a preferred embodiment of the present invention, the organic electroluminescent composition may be used as a luminescent layer preferably for the preparation of an organic electroluminescent device.
In another aspect, the present invention provides an organic electroluminescent device comprising an anode and a cathode and an organic thin film layer interposed between the anode and the cathode, the organic thin film layer comprising a light emitting layer, an optional hole injection layer, an optional hole transport layer, an optional electron injection layer, wherein at least one of the light emitting layer, the electron injection layer, the electron transport layer, the hole injection layer comprises the organic electroluminescent composition described above.
In the present invention, the organic electroluminescent composition may be used as a functional material in at least one of a light emitting layer, an electron injection layer, an electron transport layer, a hole transport layer, and a hole injection layer of an organic electroluminescent device.
In a certain embodiment of the invention, the material of the light emitting layer in the organic electroluminescent device comprises an organic electroluminescent composition as described above.
In one embodiment of the present invention, the organic electroluminescent composition is a light-emitting layer, and the light-emitting principle of the light-emitting layer is based on energy transfer from a host material to any of the compounds represented by formula I or carrier capture by the light-emitting material itself.
In one embodiment of the present invention, the organic electroluminescent device further comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer sequentially formed on the substrate; the organic light-emitting functional layer comprises a light-emitting layer containing the organic electroluminescent composition, and can also comprise any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer.
In another aspect, the present invention provides an application of the organic electroluminescent device in an organic electroluminescent display or an organic electroluminescent illumination source.
Description of the terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "comprising" or "including" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
Definition of groups
In this specification, groups and substituents thereof can be selected by one skilled in the art to provide stable moieties and compounds. When substituents are described by conventional formulas written from left to right, the substituents also include chemically equivalent substituents obtained when writing formulas from right to left.
The section headings used in this specification are for organizational purposes only and are not to be construed as limiting the subject matter described. All documents or portions of documents cited in this disclosure, including but not limited to patents, patent applications, articles, books, operating manuals, and treatises, are hereby incorporated by reference in their entirety.
Unless otherwise specified, all technical and scientific terms used herein have the standard meaning of the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.
As used herein, the singular forms "a", "an", and "the" are understood to include plural referents unless the context clearly dictates otherwise. Furthermore, the term "comprising" is an open-ended limitation and does not exclude other aspects, i.e. it includes the content indicated by the invention.
Unless otherwise indicated, the present invention employs conventional methods of mass spectrometry, elemental analysis, and the various steps and conditions are referred to in the art by conventional procedures and conditions.
The present invention employs, unless otherwise indicated, standard nomenclature for analytical chemistry, organic synthetic chemistry and optics, and standard laboratory procedures and techniques. In some cases, standard techniques are used for chemical synthesis, chemical analysis, and light emitting device performance detection.
The compounds of the present invention may contain non-natural proportions of atomic isotopes on one or more of the atoms comprising the compounds. For example, compounds such as deuterium (2H) may be labeled with a radioisotope. All isotopic variations of the compounds of the present invention, whether radioactive or not, are intended to be encompassed within the scope of the present invention.
In the present invention, the number of "substitutions" may be one or more unless otherwise specified; when plural, it means two or more, for example, may be 2, 3 or 4. In addition, when the number of "substitutions" is plural, the "substitutions" may be the same or different. In the present invention, the "substituted" position may be any position unless otherwise specified.
In the present invention, as part of a group or other groups (e.g., as used in halogen-substituted alkyl groups and the like), the term "alkyl" is meant to include both branched and straight-chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. For example, C 1 ～C 20 Alkyl groups include straight or branched chain alkyl groups having 1 to 20 carbon atoms. As in "C 1 ～C 6 Alkyl "is defined to include groups having 1, 2, 3, 4, 5, or 6 carbon atoms in a straight or branched chain structure. For example, in the present invention, the C 1 ～C 6 Alkyl is each independently methyl, ethyl, propyl, butyl, pentyl or hexyl; wherein propyl is C 3 Alkyl (including isomers such as n-propyl or isopropyl); butyl is C 4 Alkyl groups (including isomers and isomers thereof,such as n-butyl, sec-butyl, isobutyl or tert-butyl); pentyl is C 5 Alkyl (including isomers such as n-pentyl, 1-methyl-butyl, 1-ethyl-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, isopentyl, t-pentyl or neopentyl); hexyl is C 6 Alkyl (including isomers such as n-hexyl or isohexyl).
The term "alkoxy" as used herein refers to an alkyl group as defined above, each attached via an oxygen bond (-O-).
In the present invention, as part of a group or other group, the term "Cn-m aryl" refers to a monocyclic or polycyclic aromatic group having n to m ring carbon atoms (the ring atoms being carbon atoms only) having at least one carbocyclic ring having a conjugated pi electron system, wherein the polycyclic may comprise a fused (parallel ring), bridged (bridged ring), or spiro (spiro) ring system. Examples of the above aryl unit include, but are not limited to, phenyl, naphthyl, indenyl, azulenyl, fluorenyl, phenanthryl, anthracenyl, spirobifluorenyl.
In the present invention, the term "n-m membered heteroaryl" as part of a group or other group means an aromatic group having one or more (e.g., 1, 2, 3 and 4) heteroatoms selected from nitrogen, oxygen and sulfur, having from n to m ring atoms, said heteroaryl being a monocyclic, bicyclic, tricyclic or tetracyclic ring system, wherein at least one ring is an aromatic ring. Heteroaryl groups within the scope of this definition include, but are not limited to: acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazole, furanyl, thienyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, tetrahydroquinolinyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, isothiazolyl, furazanyl, thiadiazolyl, oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, purinyl, pteridinyl, naphthyridinyl, quinazolinyl, phthalazinyl, imidazopyridinyl, imidazothiazolyl, imidazooxazolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, isoindolyl, indazolyl, pyrrolopyridinyl, thienopyridinyl, benzothiadiazolyl, benzoxadiazolyl, pyrrolopyrimidinyl, thienofuranyl. In one embodiment, as preferable examples of the "5-to 18-membered heteroaryl group", furyl, thienyl, pyrrolyl, imidazolyl, thiazolyl, pyrazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyridyl, pyrimidinyl and carbazolyl groups are cited, and carbazolyl groups are more preferable.
As used herein, the term "Cn-Cm cycloalkyl" refers to a monocyclic or multicyclic alkyl group having n to m carbon atoms, e.g., C 3 -C 10 Cycloalkyl and C 3 -C 6 Cycloalkyl groups. Examples include adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and bicycloheptyl. In one embodiment, C 3 -C 10 Cycloalkyl is preferably adamantyl or cyclohexyl.
The definition of a carbon number range for a group as described in the present application means that any integer included in the definition, such as C, of carbon atoms 1 ～C 20 It is meant that the number of carbon atoms of the radical may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, C 3 -C 10 It is meant that the number of carbon atoms of the group may be 3, 4, 5, 6, 7, 8, 9 or 10, and so on for the other groups.
Those skilled in the art will appreciate that, in accordance with the convention used in the art, the present application describes the structural formula of the group usedMeaning that the corresponding group is linked to other fragments, groups in the compound through this site.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present application can be obtained.
The reagents and materials used in the present application are commercially available.
Compared with the prior art, the invention has the following beneficial effects:
the boron nitride compound adopts a binuclear strategy to realize effective red shift of a BN derivative spectrum, has a narrow spectrum, is used as a narrow spectrum luminescent material for preparing a luminescent layer of an organic electroluminescent device, realizes narrow spectrum TADF emission, and ensures that the electroluminescent external quantum efficiency of the device is up to more than 24 percent.
Drawings
Fig. 1 is a schematic view of a device structure used in an effect embodiment, in which 1 is an ITO anode, 2 is a hole injection layer, 3 is a hole transport layer, 4 is a light emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, and 7 is a metal cathode.
FIG. 2 shows the result of the reaction of Compound BN31 in toluene (concentration: 1X10 -5 M) photoluminescence spectrum in the sample.
FIG. 3 is the electroluminescent spectrum of Compound BN31 (luminescent layer: H1-33+3wt% B31).
FIG. 4 shows the result of the compound BN37 in toluene (concentration: 1X10 -5 M) photoluminescence spectrum in the sample.
FIG. 5 is the electroluminescent spectrum of Compound BN37 (luminescent layer: H1-33+3wt% B37).
FIG. 6 shows the result of the reaction of Compound BN41 in toluene (concentration: 1X 10) -5 M) photoluminescence spectrum in the sample.
FIG. 7 is an electroluminescent spectrum of Compound BN41 (luminescent layer: H1-33+3wt% B41).
FIG. 8 shows the result of the reaction of Compound BN45 in toluene (concentration: 1X10 -5 M) photoluminescence spectrum in the sample.
FIG. 9 is an electroluminescent spectrum of Compound BN45 (luminescent layer: H1-33+3wt% B45).
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Synthetic examples
The basic process route of the compound synthesis related by the invention is as follows: the preparation method comprises the steps of taking BN-M-i as a substrate, firstly obtaining a precursor BN-M-i-Br through one-step general NBS bromination reaction, and then obtaining a final product BNxx through one-step Suzuki reaction and aryl boric acid Bxx catalytic coupling. The specific synthesis process comprises the following steps:
wherein, the liquid crystal display device comprises a liquid crystal display device,
in the first step, 3mmol BN-M-i was dissolved in 20mL dry chloroform and 0.64g NBS (1.2 mmol) was slowly added to the above system under ice water bath. Liquid nitrogen is degassed and displaced for 30min. Then slowly warmed to room temperature and the reaction was continued for 4h. The reaction mixture was extracted with dichloromethane and water, the organic phase was dried by heating under vacuum and then purified by column chromatography to give the precursor BN-M-i-Br (i=1-12).
Second step, arylboronic acid/ester compound (B1-B15) (2 mmol), precursor BN-M-i-Br (1 mmol), 0.85g potassium phosphate (4 mmol) were added to dry toluene (20 mL), the mixture was bubbled with nitrogen for 10 min, and 0.22g Pd was added under high flow of nitrogen 2 (dba) 3 (0.05 mmol) and 0.4. 0.4g S-Phos (0.1 mmol). The mixture was heated to 90 ℃ and stirred for 16 hours. After the reaction system was cooled to room temperature, the reaction mixture was extracted with dichloromethane and water, the organic phase was dried by heating under vacuum, and then purified by column chromatography to give the objective product BNn (n=1 to 180).
In the synthesis examples, specific BN-M-i are as follows:
in the synthesis examples, specific BN-M-i-Br-are as follows:
in the synthetic examples, specific BXX is as follows:
experimental details of the synthetic examples are illustrated by the compound BN 37:
in the first step, 2.16g of BN-M-3 (3 mmol) was dissolved in 20mL of dry chloroform, and 640mg of NBS (1.2 mmol) was slowly added to the above system under ice water bath. Liquid nitrogen is degassed and displaced for 30min. Then slowly warmed to room temperature and the reaction was continued for 4h. The reaction mixture was extracted with dichloromethane and water, and the organic phase was dried by heating under vacuum, and then purified by column chromatography to give 1.6g of BN-M-3-Br as a precursor.
Second step, 0.91g of B7 (2 mmol), 0.72g of BN-M-3-Br (1 mmol), 0.85g of potassium phosphate (4 mmol) are added to dry toluene (20 mL), the mixture is bubbled with nitrogen for 10 min, and 0.2235g of Pd are added under high flow of nitrogen 2 (dba) 3 (0.05 mmol) and 0.41g S-Phos (0.1 mmol). The mixture was heated to 90 ℃ and stirred for 16 hours. After the reaction system was cooled to room temperature, the reaction mixture was extracted with dichloromethane and water, and the organic phase was dried by heating under vacuum, and then purified by column chromatography to obtain 0.5g of the objective product BN37.
The data on the target compounds obtained in the remaining synthesis examples are shown in Table 1.
Table 1: synthesis example product data summary
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Effect examples
Some representative electroluminescent device embodiments are given below, and some of the material molecular structures involved in the device embodiments are as follows:
c in Poly-HTL 8 H 17 Is n-octyl
The following embodiment of electroluminescent devices prepared by using the material of the present invention, the specific device preparation process is as follows:
(1) And (3) substrate processing: the transparent ITO glass is used as a substrate material for preparing devices, is subjected to ultrasonic treatment for 30min by using 5% ITO washing liquid, is sequentially subjected to ultrasonic washing by using distilled water (2 times), acetone (2 times) and isopropanol (2 times), and is finally stored in isopropanol. Before each use, the surface of the ITO glass is carefully wiped by acetone cotton balls and isopropanol cotton balls, and after the isopropanol is washed, the ITO glass is dried, and then is treated by plasma for 5min for standby. The preparation of the device is completed by combining spin coating and vacuum evaporation process.
(2) Hole injection lamination hole transport layer preparation: a layer of 20nm thick PEDOT PSS (Poly 3, 4-ethylenedioxythiophene) polystyrene sulfonate, which is commercially available from Heraeus Corp. Germany, was first spin-coated on the ITO surface as a hole injection layer, then a 50nm thick Poly-HTL was spin-coated on the hole injection layer as a hole transport layer, and then the ITO glass with the hole injection layer and the hole transport layer was annealed at 200℃for 30 minutes in a nitrogen-protected glove box (cross-linking the Poly-HTL).
(3) Preparing a light-emitting layer: the main material and the luminescent material are dissolved in dimethylbenzene according to the proportion of 97wt% (weight percent concentration) to prepare a solution with the concentration of 2wt%, and the prepared solution is used for preparing the luminescent layer by spin coating, wherein the thickness of the luminescent layer is 50nm.
(4) Preparation of an electron transport layer, an electron injection layer and a metal electrode: an electron transport layer, an electron injection layer and a metal electrode are prepared by adopting an evaporation process, and when the vacuum degree of a vacuum evaporation system reaches 5 multiplied by 10 -4 And starting evaporation when Pa is lower, wherein the deposition rate is equal to or lower than that of the Sien film thickness meter, and sequentially depositing an organic electronic transmission layer, a LiF electron injection layer and a metal Al electrode on the light-emitting layer by utilizing a vacuum evaporation process (the specific device structure is shown in the following effect example). Wherein the deposition rate of the organic material is Deposition rate of LiF->The deposition rate of Al is->
Device examples N1-1 to N1-108
In the organic electroluminescent devices (structure shown in FIG. 1) in device examples N1-1 to N1-108, ITO was used as anode 1, PEDOT: PSS was used as hole injection layer 2, poly-HTL was used as hole transport layer 3, H1-33 was used as host material in light-emitting layer 4, BNn was used as doped light-emitting material (doping concentration of 2 wt%), TRZ-8 was used as electron transport layer 5, liF was used as electron injection layer 6, and Al was used as metal cathode 7, respectively. Effect example the organic electroluminescent device structure was [ ITO/PEDOT: PSS (20 nm)/Poly-HTL (50 nm)// H1-33+3wt% bnn/TRZ-8 (50 nm)/LiF (1 nm)/Al (100 nm) ].
The current, voltage, brightness, luminescence spectrum and other characteristics of the device were synchronously tested using a Photo Research PR 655 spectral scanning luminance meter and a Keithley K2400 digital source meter system. The performance test of the device was performed at room temperature under ambient atmosphere. The External Quantum Efficiency (EQE) of the device is calculated from the current density, brightness and electro-spectral combined with the visual function in the case of the light emission as a langerhans distribution. The device life test adopts a cross-flow driving mode, and the initial brightness is 1000cd/m 2 The lifetime T90 of the device refers to the brightness of the device from 1000cd/m 2 Down to 900cd/m 2 The time (hours) elapsed during the process.
The test results are shown in Table 2.
Comparative device examples R1-1 to R1-9
Some representative comparative electroluminescent device examples are given below, and some of the luminescent material molecular structures involved in the comparative device examples are as follows:
in the organic electroluminescent devices (structure shown in FIG. 1) in comparative device examples R1-1 to R1-9, ITO was used as anode 1, PEDOT: PSS was used as hole injection layer 2, poly-HTL was used as hole transport layer 3, H1-33 was used as host material in light-emitting layer 4, R1 to R9 were used as doped light-emitting materials (doping concentration was 2 wt%), TRZ-8 was used as electron transport layer 5, liF was used as electron injection layer 6, and Al was used as metal cathode 7, respectively. Effect example the organic electroluminescent device structure was [ ITO/PEDOT: PSS (20 nm)/Poly-HTL (50 nm)// H1-33+3wt% r-r/TRZ-8 (50 nm)/LiF (1 nm)/Al (100 nm) ] (r=1-9).
The current, voltage, brightness, luminescence spectrum and other characteristics of the device were synchronously tested using a Photo Research PR 655 spectral scanning luminance meter and a Keithley K2400 digital source meter system. The performance test of the device was performed at room temperature under ambient atmosphere. The External Quantum Efficiency (EQE) of the device is calculated from the current density, brightness and electro-spectral combined with the visual function in the case of the light emission as a langerhans distribution. The device life test adopts a cross-flow driving mode, and the initial brightness is 1000cd/m 2 The lifetime T90 of the device refers to the brightness of the device from 1000cd/m 2 Down to 900cd/m 2 The time (hours) elapsed during the process.
The test results are shown in Table 3.
Table 2: device examples N1-1 to N1-108 data
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Table 3: comparative device examples R1-1 to R1-9 data
The electroluminescent device effect implementation data listed in table 2 prove that the luminescent material provided by the invention can be used for preparing high-efficiency organic electroluminescent devices, the electroluminescent spectrum has narrow band characteristics, the half-width of the electroluminescent spectrum is less than 45nm, the electroluminescent external quantum efficiency is as high as more than 38.5%, and the service life of the devices is more than 98.5 hours.
Device examples N2-1 to N2-108
In the organic electroluminescent devices (structure shown in FIG. 1) in device examples N2-1 to N2-108, ITO was used as anode 1, PEDOT: PSS was used as hole injection layer 2, poly-HTL was used as hole transport layer 3, a mixture of H1-33 and TRZ-8 in light-emitting layer 4 was used as host material (weight mixing ratio of H1-33 and TRZ-8 was 1:1), BNn was used as doped light-emitting material (doping concentration was 3 wt%), TRZ-8 was used as electron transport layer 5, liF was used as electron injection layer 6, and Al was used as metal cathode 7, respectively. Effect example the organic electroluminescent device structure was [ ITO/PEDOT: PSS (20 nm)/Poly-HTL (50 nm)/H1-33:trz-8+3wt% bnn/TRZ-8 (50 nm)/LiF (1 nm)/Al (100 nm) ].
The current, voltage, brightness, luminescence spectrum and other characteristics of the device were synchronously tested using a Photo Research PR 655 spectral scanning luminance meter and a Keithley K2400 digital source meter system. The performance test of the device was performed at room temperature under ambient atmosphere. The External Quantum Efficiency (EQE) of the device is calculated from the current density, brightness and electro-spectral combined with the visual function in the case of the light emission as a langerhans distribution. The device life test adopts a cross-flow driving mode, and the initial brightness is 1000cd/m 2 The lifetime T90 of the device refers to the brightness of the device from 1000cd/m 2 Down to 900cd/m 2 The time (hours) elapsed during the process.
The test results are shown in Table 4.
Comparative device examples R2-1 to R2-9
In the organic electroluminescent devices (structure shown in FIG. 1) in device examples R2-1 to R2-9, ITO was used as anode 1, PEDOT: PSS was used as hole injection layer 2, poly-HTL was used as hole transport layer 3, a mixture of H1-33 and TRZ-8 in light-emitting layer 4 was used as host material (weight mixing ratio of H1-33 and TRZ-8 was 1:1), R1 to R9 were used as doped light-emitting materials (doping concentration was 3 wt%), TRZ-8 was used as electron transport layer 5, liF was used as electron injection layer 6, and Al was used as metal cathode 7, respectively. Effect example the organic electroluminescent device structure was [ ITO/PEDOT: PSS (20 nm)/Poly-HTL (50 nm)/H1-33: trz-8+3wt% r-r/TRZ-8 (50 nm)/LiF (1 nm)/Al (100 nm) ] (r=1-9).
The current, voltage, brightness, luminescence spectrum and other characteristics of the device were synchronously tested using a Photo Research PR 655 spectral scanning luminance meter and a Keithley K2400 digital source meter system. The performance test of the device was performed at room temperature under ambient atmosphere. The External Quantum Efficiency (EQE) of the device is calculated from the current density, brightness and electro-spectral combined with the visual function in the case of the light emission as a langerhans distribution. The device life test adopts a cross-flow driving mode, and the initial brightness is 1000cd/m 2 The lifetime T90 of the device refers to the brightness of the device from 1000cd/m 2 Down to 900cd/m 2 The time (hours) elapsed during the process.
The test results are shown in Table 5.
Table 4: device examples N2-1 through N2-108 data
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Table 5: comparative device examples R2-1 to R2-9 data
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The electroluminescent device effect implementation data listed in table 4 prove that the luminescent material provided by the invention can be used for preparing high-efficiency organic electroluminescent devices, the electroluminescent spectrum has narrow band characteristics, the half-width of the electroluminescent spectrum is less than 45nm, the electroluminescent external quantum efficiency is as high as more than 38.5%, and the service life of the device is more than 104.5 hours.
The applicant states that the present invention is illustrated by the above examples of boron nitride compounds of the present invention and their use, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (13)
1. A boron nitrogen heterocyclic compound shown in a formula I,
wherein, -E-represents a C-C single bond, i.e. the R group is linked to the benzene ring by a C-C single bond;
r is independently C 6 ～C 30 Aryl, 5-36 membered heteroaryl, substituted with one or more R m1 Substitution C 6 ～C 30 Aryl, or substituted by one or more R m1 Substituted 5-36 membered heteroaryl;
R m1 independently at each occurrenceH, D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, substituted by one or more R m2 Substituted C 1 ～C 20 Alkyl, C 3 ～C 12 Cycloalkyl, C 1 ～C 12 Alkoxy, C 6 ～C 18 Aryl, 5-30 membered heteroaryl, diphenylamino, substituted with one or more R m2 Substitution C 6 ～C 18 Aryl, substituted by one or more R m2 Substituted with 5-to 30-membered heteroaryl, or with one or more R m2 Substituted diphenylamino groups;
R m2 each occurrence is independently H, D (deuterium), fluorine, CN, biphenyl, C 1 ～C 12 Alkyl, C 6 ～C 18 Aryl substituted C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 6 ～C 18 Aryl or 5-18 membered heteroaryl;
R 1 and R is 2 H, D (deuterium), fluorine, CN, C independently 1 ～C 20 Alkyl, substituted by one or more R a Substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Alkoxy, C 3 ～C 12 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R a Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R a Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R a Substituted diphenylamino groups;
R a each occurrence is independently D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, substituted by one or more R b Substituted C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 12 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R b Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R b Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R b Substituted diphenylamino groups;
R b independently at each occurrence D (deuterium),Fluorine, CN, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R c Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R c Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R c Substituted diphenylamino groups;
R c each occurrence is independently D (deuterium), fluorine, CN, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 3 ～C 10 Cycloalkyl, C 6 ～C 18 Aryl, substituted by one or more R d Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R d Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R d Substituted diphenylamino groups;
R d each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy, C 6 ～C 18 Aryl or by one or more R e Substituted C 6 ～C 18 An aryl group;
R e each occurrence is independently D (deuterium), fluorine, C 1 ～C 12 Alkyl, C 1 ～C 12 Alkoxy or C 6 ～C 14 An aryl group;
the aryl and heteroaryl are independently monocyclic, fused or spiro;
The number of heteroatoms in the heteroaryl is independently 1, 2 or 3, and each heteroatom is independently N, O or S.
2. The boron nitride heterocyclic compound of formula I as described in claim 1,
R m1 each occurrence is independently CN, C 6 ～C 18 Aryl, 5-30 membered heteroaryl, diphenylamino, substituted with one or more R m2 Substitution C 6 ～C 18 Aryl, covered by one or moreR m2 Substituted with 5-to 30-membered heteroaryl, or with one or more R m2 Substituted diphenylamino groups;
and/or R m2 At each occurrence independently is biphenyl, C 1 ～C 12 Alkyl, C 6 ～C 18 Aryl substituted C 1 ～C 12 Alkyl or C 6 ～C 18 An aryl group;
and/or, the R 1 And R is 2 H, C independently 1 ～C 20 Alkyl, substituted by one or more R a Substituted C 1 ～C 20 Alkyl, C 6 ～C 18 Aryl, substituted by one or more R a Substituted C 6 ～C 18 Aryl, 5-18 membered heteroaryl, substituted with one or more R a Substituted 5-18 membered heteroaryl, diphenylamino, or substituted with one or more R a Substituted diphenylamino groups;
and/or, the R a Independently at each occurrence C 1 ～C 12 Alkyl, substituted by one or more R b Substituted C 1 ～C 12 Alkyl or C 6 ～C 18 An aryl group;
and/or, the R b Independently at each occurrence C 6 ～C 18 Aryl groups.
3. The boron nitride heterocyclic compound as described in claim 2, wherein,
In the definition of R, the C 6 ～C 30 Aryl is independently at each occurrence C 6 ～C 25 An aryl group;
and/or, in the definition of R, the 5-36 membered heteroaryl is independently at each occurrence a 5-26 membered heteroaryl, wherein the number of heteroatoms is 1, and the heteroatoms are N or O;
and/or, the R m1 In the definition of (C), said C 6 ～C 18 Aryl is independently at each occurrence C 6 ～C 13 An aryl group;
and/or, the R m1 In the definition of (2), the 5-30 membered heteroaryl is independently at each occurrenceIs a 5-26 membered heteroaryl;
and/or, the R m2 In the definition of (C), said C 6 ～C 18 Aryl is independently at each occurrence phenyl;
and/or, the R m2 In the definition of (C), said C 1 ～C 12 Alkyl is independently at each occurrence isopropyl or tert-butyl;
and/or, the R 1 And R is 2 In the definition of (C), said C 6 ～C 18 Aryl is independently at each occurrence phenyl;
and/or, the R 1 And R is 2 In the definition of (2), the 5-18 membered heteroaryl is independently at each occurrence a 5-13 membered heteroaryl, wherein the number of heteroatoms is 1 and the heteroatoms are N;
and/or, the R a In the definition of (C), said C 1 ～C 12 Alkyl is independently at each occurrence methyl, isopropyl or tert-butyl;
and/or, the R a In the definition of (C), said C 6 ～C 18 Aryl is independently at each occurrence phenyl;
And/or, the R b In the definition of (C), said C 6 ～C 18 Aryl is independently phenyl at each occurrence.
4. The boron nitride heterocyclic compound according to claim 3, wherein the boron nitride heterocyclic compound is represented by formula I,
in the definition of R, the C 6 ～C 30 Aryl is independently at each occurrence phenyl or spirobifluorenyl;
and/or, in the definition of R, the 5-36 membered heteroaryl is independently at each occurrence a carbazolyl or spirofluorenyl oxaanthracenyl;
and/or, the R m1 In the definition of (C), said C 6 ～C 18 Aryl is independently at each occurrence phenyl or fluorenyl;
and/or, the R m1 In the definition of (2), the 5-30 membered heteroaryl is independently at each occurrence pyrimidinyl, triazinyl, carbazolyl, 5H-pyridoindolyl,9, 10-dihydroacridinyl, phenothiazinyl, phenoxazinyl or spirofluorene azaanthracyl;
and/or, the R 1 And R is 2 In the definition of (2), the 5-18 membered heteroaryl is independently carbazolyl for each occurrence;
and/or, the R 1 And R is 2 In the definition of (2), said R a Is H, methyl, isopropyl, tert-butyl or
5. The boron nitride heterocyclic compound of formula I as described in claim 4,
the R is any one structure from R-R1 to R-R26:
and/or, the R 1 And R is 2 Independently H, methyl, Phenyl group,/->
6. The boron nitride heterocyclic compound according to claim 1, represented by formula I, which is any one of the following compounds:
/>
/>
/>
/>
/>
/>
7. the process for preparing a boron nitrogen heterocyclic compound as described in any one of claims 1 to 6, which is represented by the formula I, characterized by comprising the steps of: carrying out the following Suzuki reaction on a compound shown in a formula II and a compound shown in a formula III to obtain the boron nitrogen heterocyclic compound shown in the formula I;
wherein Hal is halogen, E, R, R 1 And R is 2 Is as defined in any one of claims 1 to 6.
8. The organic electroluminescent composition is characterized by comprising a doping material and a host material, wherein the doping material comprises the boron-nitrogen heterocyclic compound shown in the formula I;
preferably, the doping material is present in an amount of 0.3-30.0wt%, for example 3wt%; the host material is present in an amount of 99.7 to 70.0wt%, for example 97%; wt% means the weight percentage of each component in the organic electroluminescent composition;
preferably, the organic electroluminescent composition is used as a light emitting layer for preparing an organic electroluminescent device.
9. The organic electroluminescent composition according to claim 8, wherein the host material comprises a material a and/or a material B, the material a comprising a carbazole derivative and/or a carboline derivative, and the material B comprising a pyrimidine derivative and/or a triazine derivative.
10. The organic electroluminescent composition according to claim 9, wherein the host material comprises a material a and a material B, wherein the weight ratio of the material a to the material B is 1:5 to 5:1;
and/or the material A comprises one or more of compounds shown as the formula H-1, H-2, H-3, H-4, H-5, H-6 or H-7,
/>
wherein X is 1 、Y 1 And Z 1 Is CH or N, and X 1 、Y 1 And Z 1 At most one of them is N;
R 1H and R is 2H Independently is any one of the following structures:
wherein X is 2 、Y 2 And Z 2 Is CH or N, and X 2 、Y 2 And Z 2 At most one of them is N;
R aH and R is bH H, C independently 1 ～C 20 Alkyl, C 1 ～C 20 Alkoxy, C 6 ～C 20 Aryl, C 1 ～C 20 Alkyl substituted C 6 ～C 20 Aryl or C 1 ～C 20 Alkoxy substituted C 6 ～C 20 An aryl group;
for example, the number of the cells to be processed,/>
and/or the material B comprises one or more of the compounds shown as the formula Trz1-A, trz2-A, trz3-A, trz4-A, trz5-A or Trz6-A,
wherein R is 1a 、R 1b 、R 2a 、R 2b 、R 3a And R is 3b Wherein 1 or 2 are independently R Tz The remainder are independently hydrogen, deuterium, C 1 ～C 8 Alkyl, C 1 ～C 8 Alkoxy, C 6 ～C 18 Aryl, C 1 ～C 8 Alkyl substituted C 6 ～C 18 Aryl or C 1 ～C 8 Alkoxy substituted C 6 ～C 18 Aryl of (a);
R Tz independently any of the groups shown below:
/>
/>
wherein the asterisks represent the attachment site of the group;
for example, the number of the cells to be processed,
11. use of a boron nitride compound of the formula I as claimed in any one of claims 1 to 6 or an organic electroluminescent composition as claimed in any one of claims 8 to 10 as an organic electroluminescent material,
The boron-nitrogen compound shown in the formula I can be used as a doped luminescent material; and/or the organic electroluminescent composition can be used as a luminescent layer for preparing an organic electroluminescent device.
12. An organic electroluminescent device comprising an anode and a cathode and an organic thin film layer disposed between the anode and the cathode, the organic thin film layer comprising a light emitting layer, an optional hole injection layer, an optional hole transport layer, an optional electron transport layer, and an optional electron injection layer, wherein at least one of the light emitting layer, the electron injection layer, the electron transport layer, the hole transport layer, and the hole injection layer is the organic electroluminescent composition of any one of claims 8 to 10.
13. Use of an organic electroluminescent device as claimed in claim 12 in an organic electroluminescent display or an organic electroluminescent illumination source.
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