CN116143737A - Compound with anthracene-linked asymmetric dibenzoheterocycle and application thereof - Google Patents
Compound with anthracene-linked asymmetric dibenzoheterocycle and application thereof Download PDFInfo
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- CN116143737A CN116143737A CN202111352622.7A CN202111352622A CN116143737A CN 116143737 A CN116143737 A CN 116143737A CN 202111352622 A CN202111352622 A CN 202111352622A CN 116143737 A CN116143737 A CN 116143737A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 84
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 57
- -1 pyridopyrazinyl Chemical group 0.000 claims description 34
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 31
- 229910052805 deuterium Inorganic materials 0.000 claims description 31
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 30
- 125000001072 heteroaryl group Chemical group 0.000 claims description 28
- 150000002431 hydrogen Chemical class 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 25
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000004305 biphenyl Substances 0.000 claims description 15
- 235000010290 biphenyl Nutrition 0.000 claims description 15
- 125000001624 naphthyl group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000005580 triphenylene group Chemical group 0.000 claims description 12
- 125000001769 aryl amino group Chemical group 0.000 claims description 10
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 10
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 claims description 10
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 10
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 10
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 10
- 125000002541 furyl group Chemical group 0.000 claims description 10
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 10
- 125000005561 phenanthryl group Chemical group 0.000 claims description 10
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 10
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 10
- 125000004076 pyridyl group Chemical group 0.000 claims description 10
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 10
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 10
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 10
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 10
- 125000001544 thienyl group Chemical group 0.000 claims description 10
- 125000004306 triazinyl group Chemical group 0.000 claims description 10
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 125000005549 heteroarylene group Chemical group 0.000 claims description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 4
- 125000006716 (C1-C6) heteroalkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 2
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YEYHFKBVNARCNE-UHFFFAOYSA-N pyrido[2,3-b]pyrazine Chemical compound N1=CC=NC2=CC=CN=C21 YEYHFKBVNARCNE-UHFFFAOYSA-N 0.000 claims description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005556 thienylene group Chemical group 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 92
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- 238000006243 chemical reaction Methods 0.000 description 304
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 210
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 148
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 128
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 106
- 229910000027 potassium carbonate Inorganic materials 0.000 description 74
- 239000000843 powder Substances 0.000 description 74
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 46
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 38
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- 238000004809 thin layer chromatography Methods 0.000 description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 20
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 20
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 19
- 238000001704 evaporation Methods 0.000 description 19
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 18
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 18
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- 238000005406 washing Methods 0.000 description 9
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 8
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- VHHDLIWHHXBLBK-UHFFFAOYSA-N anthracen-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=CC2=C1 VHHDLIWHHXBLBK-UHFFFAOYSA-N 0.000 description 7
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- GGTUVWGMCFXUAS-UHFFFAOYSA-N (5-chloro-2-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=CC=C1F GGTUVWGMCFXUAS-UHFFFAOYSA-N 0.000 description 5
- WGAVMKXCDMQVNF-UHFFFAOYSA-N 5-chloro-2-fluorobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=CC=C1F WGAVMKXCDMQVNF-UHFFFAOYSA-N 0.000 description 5
- YPNZWHZIYLWEDR-UHFFFAOYSA-N 9-naphthalen-1-ylanthracene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=C(C=CC=C3)C3=CC2=C1 YPNZWHZIYLWEDR-UHFFFAOYSA-N 0.000 description 4
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- LUBXLGUQZVKOFP-UHFFFAOYSA-N 9-phenylanthracene Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=CC2=CC=CC=C12 LUBXLGUQZVKOFP-UHFFFAOYSA-N 0.000 description 2
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- UMLDUMMLRZFROX-UHFFFAOYSA-N pyridin-2-ylboronic acid Chemical compound OB(O)C1=CC=CC=N1 UMLDUMMLRZFROX-UHFFFAOYSA-N 0.000 description 1
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
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Abstract
The application provides a compound of the general formula (I), which has a parent structure of an anthracene-linked asymmetric dibenzoheterocycle, has high bond energy among atoms, good thermal stability and is favorable for solid state accumulation among molecules, and simultaneously, has large bandwidth, high luminous intensity and proper energy level between adjacent layers, and is favorable for exciton injectionIngress and migration. When the organic light-emitting diode is used as a blue light main body material in a light-emitting layer, the driving voltage of the organic light-emitting diode can be effectively reduced, the light-emitting efficiency of the organic light-emitting diode can be improved, and the service life of the organic light-emitting diode can be prolonged. The application also provides an organic electroluminescent device and a display device comprising the compound of the general formula (I).
Description
Technical Field
The application relates to the technical field of organic light-emitting display, in particular to a compound with an anthracene-linked asymmetric dibenzoheterocycle and application thereof.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, etc., compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, the response speed can reach 1000 times of the liquid crystal display, and the manufacturing cost is lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advancement of OLED technology in the two fields of illumination and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is usually the result of the optimized collocation of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the film can be formed on any substrate by vapor deposition or spin coating, flexible display and large-area display can be realized, and the optical performance, the electrical performance, the stability and the like of the material can be adjusted by changing the molecular structure, so that the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (including host materials and guest materials), etc., and the most important factor determining the light emitting efficiency of the OLED is the light emitting material.
Disclosure of Invention
The object of the present application is to provide a compound having an anthracene-linked asymmetric dibenzoheterocycle, which can achieve an improvement in the operating efficiency and an extension in the service life of an organic electroluminescent device when used as an organic light emitting material.
The first aspect of the present application provides a compound of formula (I):
wherein,,
Ar 1 or Ar 2 Selected from the group consisting of
R 1 -R 5 Each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted by Rc, R 1 -R 5 Can be linked to form a ring;
R 6 -R 13 each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 6 Heteroalkyl, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted by Rc, R 6 -R 13 Can be linked to form a ring;
L 1 or L 2 Selected from the group consisting of a bond, C which is unsubstituted or substituted by Rc 6 -C 30 Arylene, C unsubstituted or substituted with Rc 3 -C 30 Heteroarylene;
m, n are selected from 0 or 1, and m+n=1;
X 1 -X 5 each independently selected from CR or N, each R is independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R can be linked to form a ring;
Y 1 -Y 5 each independently selected from CR 'or N, each R' is independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R' can be linked to form a ring;
z is selected from O, S or CRaRb, ra and Rb are each independently selected from C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, said Ra and said Rb being capable of being linked to form a ring;
the heteroatoms on the heteroaryl or the heteroalkyl are each independently selected from O, S or N;
the substituents Rc of each group are each independently selected from deuterium, halogen, nitro, cyanoRadical, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
A second aspect of the present application provides an organic light-emitting material comprising at least one of the compounds provided in the first aspect of the present application.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the organic luminescent materials provided in the second aspect of the present application.
A fourth aspect of the present application provides a display device comprising the organic electroluminescent device provided in the third aspect of the present application.
The compound provided by the application has the parent structure of the anthracene-linked asymmetric dibenzoheterocycle, has high bond energy among atoms, good thermal stability, is favorable for solid-state accumulation among molecules, and meanwhile, has large bandwidth, and a light-emitting area is positioned in a blue light area and has high light-emitting intensity. When the blue light host material is applied to a light-emitting layer, the blue light host material has proper energy level with adjacent layers, is favorable for injection and migration of excitons, can effectively reduce driving voltage, has higher exciton migration rate, and can realize good light-emitting efficiency and service life in an organic electroluminescent device. The compound has a larger conjugation plane, is favorable for molecular accumulation, shows good thermodynamic stability, and shows long service life in a device. The organic electroluminescent device comprises the compound as a blue luminescent material, so that the driving voltage can be effectively reduced, the luminous efficiency can be improved, and the service life of the organic electroluminescent device can be prolonged. The display device provided by the application has excellent display effect.
Of course, not all of the above-described advantages need be achieved simultaneously in practicing any one of the products or methods of the present application.
Drawings
For a clearer description of the technical solutions of the present application or of the prior art, reference will be made below to the accompanying drawings used in the embodiments or in the description of the prior art, which are, obviously, only some embodiments of the present application, from which it is possible for a person skilled in the art to obtain other embodiments.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. Based on the embodiments herein, a person of ordinary skill in the art would be able to obtain all other embodiments based on the disclosure herein, which are within the scope of the disclosure herein.
The first aspect of the present application provides a compound of formula (I):
wherein,,
Ar 1 or Ar 2 Selected from the group consisting of
R 1 -R 5 Each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted by Rc, R 1 -R 5 Can be linked to form a ring;
R 6 -R 13 each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 6 Heteroalkyl, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted by Rc, R 6 -R 13 Can be linked to form a ring;
L 1 or L 2 Selected from the group consisting of a bond, C which is unsubstituted or substituted by Rc 6 -C 30 Arylene, C unsubstituted or substituted with Rc 3 -C 30 Heteroarylene;
m, n are selected from 0 or 1, and m+n=1;
X 1 -X 5 each independently selected from CR or N, each R is independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R can be linked to form a ring;
Y 1 -Y 5 each independently selected from CR 'or N, each R' is independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R' can be linked to form a ring;
z is selected from O, S or CRaRb, ra and Rb are each independently selected from C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, said Ra and said Rb being capable of being linked to form a ring;
the heteroatoms on the heteroaryl or the heteroalkyl are each independently selected from O, S or N;
the substituents Rc of each group are each independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Preferably Ar 1 Or Ar 2 Selected from the group consisting of
R 1 -R 5 Each independently selected from hydrogen, deuterium,C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted by Rc, R 1 -R 5 Can be linked to form a ring;
preferably, R 6 -R 13 Each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 3 Heteroalkyl, C unsubstituted or substituted with Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted by Rc, R 6 -R 13 Can be linked to form a ring;
preferably L 1 Or L 2 Selected from the group consisting of a bond, C which is unsubstituted or substituted by Rc 6 -C 30 Arylene, C unsubstituted or substituted with Rc 3 -C 30 Heteroarylene;
preferably X 1 -X 5 Each independently selected from CR or N, R is each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R can be linked to form a ring;
preferably Y 1 -Y 5 Each independently selected from CR 'or N, R' is each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R' can be linked to form a ring;
preferably, Z is selected from O, S or CRaRb, ra, rb are each independently selected from C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted with Rc, said Ra and said Rb being capable of linking to form a ring.
More preferably, R 1 -R 5 Each independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, R 6 -R 13 Each independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, each R is independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, each R' is independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably L 1 Or L 2 A subunit selected from the group consisting of a bond, unsubstituted or substituted with Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole.
More preferably, ra, rb are each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
For example, the compound of formula (I) may be selected from the compounds shown in A1 to a30 below:
the compound of the general formula (I) provided by the application has high bond energy among atoms, good thermal stability and favorability for solid accumulation among molecules. Meanwhile, the bandwidth is large, the light-emitting area is positioned in the blue light area, and the light-emitting intensity is high. In addition, the preparation process of the compound shown in the general formula (I) is simple and feasible, raw materials are easy to obtain, and the preparation process is suitable for industrial production.
A second aspect of the present application provides an organic light-emitting material comprising at least one of the compounds provided herein.
When the organic luminescent material is applied in a luminescent layer, the organic luminescent material has proper energy level with adjacent layers, is favorable for the injection and migration of excitons, and can effectively reduce driving voltage. Meanwhile, the organic electroluminescent device has higher exciton migration rate, and can realize good luminous efficiency and service life in the organic electroluminescent device. Meanwhile, the organic electroluminescent device also has a larger conjugate plane, is favorable for molecular accumulation, shows good thermodynamic stability, and can prolong the service life of the organic electroluminescent device when used in the organic electroluminescent device.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the organic luminescent materials provided herein. Therefore, the organic electroluminescent device provided by the application has low driving voltage, high luminous efficiency and long service life.
Preferably, the organic light emitting material of the present application is used as a blue host material in an organic electroluminescent device.
In the present application, the kind and structure of the organic electroluminescent device are not particularly limited, and may be organic electroluminescent devices of different types and structures known in the art, as long as the organic luminescent material provided in the present application can be used.
The organic electroluminescent device of the present application may be a light emitting device having a top emission structure, and examples thereof include an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a bottom light emitting structure, and examples thereof include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a double-sided light emitting structure, and examples thereof include a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode structure sequentially formed on a substrate.
The organic electroluminescent device can further comprise an electron blocking layer arranged between the hole transmission layer and the luminescent layer, a hole blocking layer arranged between the luminescent layer and the electron transmission layer, and a light extraction layer arranged on the transparent electrode of the light emitting layer. However, the structure of the organic electroluminescent device of the present application is not limited to the above-described specific structure, and these layers may be added or omitted depending on the specific case in practical application. The thickness of each layer is not particularly limited as long as the object of the present application can be achieved. For example, the organic electroluminescent device may include an anode electrode, a hole injection layer (5-20 nm), a hole transport layer (80-140 nm), an electron blocking layer (5-20 nm), a light emitting layer (150-400 nm), a hole blocking layer (5-20 nm), an electron transport layer (300-800 nm), an electron injection layer (5-20 nm), a transparent cathode electrode, and a light extraction layer (50-90 nm) in this order on a substrate.
Fig. 1 shows a schematic view of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are disposed in this order from bottom to top.
It will be appreciated that fig. 1 schematically illustrates only one typical organic electroluminescent device structure, and the present application is not limited to this structure, and the organic luminescent material of the present application may be used for any type of organic electroluminescent device.
For convenience, the organic electroluminescent device of the present application will be described below with reference to fig. 1, but this is not meant to limit the scope of protection of the present application in any way. It is understood that all organic electroluminescent devices capable of using the organic luminescent materials of the present application are within the scope of the present application.
In the present application, the substrate 1 is not particularly limited, and conventional substrates used in the organic electroluminescent device in the related art, for example, glass, polymer materials, glass with Thin Film Transistor (TFT) elements, polymer materials, and the like can be used.
In the present application, the reflective anode material 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) 2 ) The transparent conductive material such as zinc oxide (ZnO) may be selected from metallic materials such as silver and its alloy, aluminum and its alloy, organic conductive materials such as poly 3, 4-ethylenedioxythiophene (PEDOT), and the like, or a multilayer structure of the above materials.
In the present application, the material of the hole injection layer 3 is not particularly limited, and a hole injection layer material known in the art may be used. For example, at least one of known Hole Transport Materials (HTM) is selected as the hole injection material.
In the present application, the hole injection layer 3 may further include a p-type dopant, the kind of which is not particularly limited, and various p-type dopants known in the art may be employed. For example, the p-type dopant may be selected from, but is not limited to, at least one of the following p-1 to p-3 compounds:
in the present application, the amount of the p-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the material of the hole transport layer 4 is not particularly limited, and may be made using a Hole Transport Material (HTM) well known in the art. The number of layers of the hole transport layer 4 is not particularly limited and may be adjusted according to actual needs as long as the purpose of the present application is satisfied, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.
For example, the HTM for the hole injection layer material and the HTM for the hole transport layer material may be selected from, but are not limited to, at least one of the following HT-1 to HT-31 compounds:
in this application, the material of the light emitting layer 5 may include a host material and a guest material.
In the present application, the host material may contain at least one of the organic light emitting materials of the present application, or may contain a combination of at least one of the organic light emitting materials of the present application and at least one of the known host materials.
For example, known host materials may be selected from, but are not limited to, at least one of the following BH-1 to BH-10 compounds:
in the present application, the guest material is not particularly limited, and at least one of the light emitting layer guest materials known in the art may be used. For example, the light emitting layer guest material may be selected from, but is not limited to, at least one of the following BD-1 to BD-9 compounds:
in the present application, the amount of the guest material of the light emitting layer is not particularly limited, and may be an amount known to those skilled in the art.
In the present application, the material of the electron transport layer 6 is not particularly limited, and electron transport materials known in the art may be used. The number of layers of the electron transport layer 6 is not particularly limited and may be adjusted according to actual needs as long as the purpose of the present application is satisfied, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.
For example, known electron transport materials may be selected from, but are not limited to, at least one of the following ET-1 to ET-57 compounds:
in the present application, the electron transport layer 6 may further include n-type dopants, the kind of which is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
in the present application, the amount of the n-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, for example, may include, but not limited to, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of materials such as BaO, na, li, ca.
In the present application, the material of the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, metals such as magnesium silver mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.
A fourth aspect of the present application provides a display device, which includes the organic electroluminescent device provided herein. Including but not limited to displays, televisions, tablet computers, mobile communication terminals, etc.
The method of preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be employed, for example, the present application may be prepared using the following preparation method:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top light emission, respectively performing steps of medicine washing, water washing, hairbrushes, high-pressure water washing, air knives and the like in a cleaning machine, and then performing heating treatment;
(2) Vacuum evaporating a hole injection material on the reflective anode electrode 2 as a hole injection layer 3;
(3) Vacuum evaporating a hole transport material on the hole injection layer 3 as a hole transport layer 4;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer 5 comprises a host material and a guest material;
(5) Vacuum evaporating an electron transport material on the light-emitting layer 5 as an electron transport layer 6;
(6) Vacuum evaporating an electron injection material on the electron transport layer 6 as an electron injection layer 7;
(7) A cathode material is vacuum-evaporated on the electron injection layer 7 as a cathode electrode 8.
Only the structure of a typical organic electroluminescent device and a method of manufacturing the same are described above, and it should be understood that the present application is not limited to such a structure. The organic light emitting material of the present application may be used for an organic electroluminescent device of any structure, and the organic electroluminescent device may be prepared using any preparation method known in the art.
The method for synthesizing the compound of the present application is not particularly limited, and may be synthesized by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
Synthesis example 1 Synthesis of Compound A1
In a single flask, 100mmol of 9-phenylanthracene and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1h at 0℃and the disappearance of starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M1.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd is 2 (dba) 3 The amount of (C) added was 1mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is completed, and cooling the reactant to the chamberWarm water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 2-fluoro-4-chlorobenzoic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-4-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M5, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6.
Into a reaction flask were charged 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
In a single flask, 100mmol of M7 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M8.
Into a reaction flask were charged 100mmol of M8, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M8.
1 H NMR(400MHz,Chloroform)8.21(s,1H),8.00(s,1H),7.79(d,J＝8.0Hz,4H),7.69-7.54(m,7H),7.50(dd,J＝12.8,8.0Hz,8H),7.44(dd,J＝12.0,7.6Hz,6H),7.25(s,1H).
Synthesis example 2 Synthesis of Compound A7
In a single flask, 100mmol of 9- (1-naphthyl) anthracene and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1 hour at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M1.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd is 2 (dba) 3 The amount of (C) added was 1mol% based on M1.
100 was added to the reaction flaskmmol of M2, 100mmol of o-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water are added, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 2-fluoro-5-chlorobenzoic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-5-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M5, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6.
Into a reaction flask were charged 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is completed, and cooling the reactant to the chamberWarm water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
In a single flask, 100mmol of M7 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M8.
Into a reaction flask were charged 100mmol of M8, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M8.
1 H NMR(400MHz,Chloroform)δ8.95(s,1H),8.50(s,1H),7.96(d,J＝7.6Hz,3H),7.89(s,1H),7.78(t,J＝8.0Hz,4H),7.69(s,1H),7.65–7.55(m,10H),7.49–7.36(m,8H),7.34(s,1H).
Synthesis example 3 Synthesis of Compound A8
Into a reaction flask were charged 100mmol of 9-anthraceneboronic acid, 100mmol of deuterated bromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 9-anthraceneboronic acid.
In a single flask, 100mmol of 9- (1-naphthyl) anthracene and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1 hour at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of M5, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M5.
Into a reaction flask were charged 100mmol of 2-fluoro-5-chlorobenzoic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is completed, cooling the reactant to room temperature, adding water, filtering and washing to obtainThe solid of (2) was purified by recrystallization from toluene to give white powder M6. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-5-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M6, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7.
Into a reaction flask were charged 100mmol of M5, 100mmol of M7, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M8. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
In a single flask, 100mmol of M8 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M9.
Into a reaction flask were charged 100mmol of M9, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A8. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.21(s,1H),8.16-7.79(m,3H),7.69(d,J＝8.0Hz,4H),7.67–7.55(m,7H),7.44(dd,J＝12.4,7.6Hz,8H).
Synthesis example 4 Synthesis of Compound A13
Into a reaction flask were charged 100mmol of 9-anthraceneboronic acid, 100mmol of deuterated bromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of N, N-dimethylformamide (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 9-anthraceneboronic acid.
In a single flask, 100mmol of M1 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1h at 0℃and the disappearance of starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of 2-phenyl-4-chlorobromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M4, 100mmol of pinacol biborate, 41.4g of potassium carbonate(300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M4.
Into a reaction flask were charged 100mmol of 2-fluoro-4-chlorobenzoic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-4-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M6, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7.
Into a reaction flask were charged 100mmol of M5, 100mmol of M7, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M8. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
In a single flask, 100mmol of M8 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M9.
Adding into a reaction bottle100mmol of M9, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water are added with 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a13. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M9.
1 H NMR(400MHz,Chloroform)8.23(d,J＝12.0Hz,1H),8.08(d,J＝12.8Hz,2H),7.79(d,J＝8.0Hz,5H),7.73-7.60(m,7H),7.52(d,J＝12.0Hz,6H),7.44(dd,J＝12.4,7.6Hz,6H),7.35(s,1H).
Synthesis example 5 Synthesis of Compound A14
In a single flask, 100mmol of 9- (1-naphthyl) anthracene and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1 hour at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M1.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd is 2 (dba) 3 The amount of (C) added was 1mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of N, N-dimethylformamide (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is finished, cooling the reactant to room temperature,water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 2-fluoro-5-chlorobenzoic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-5-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M5, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6.
Into a reaction flask were charged 100mmol of M4, 200mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 2mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
In a single flask, 100mmol of M7 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M8.
Into a reaction flask were charged 100mmol of M8, 200mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 2mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a14. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M8.
1 H NMR(400MHz,Chloroform)8.95(s,1H),8.26-8.10(m,4H),7.89(s,1H),7.78(t,J＝8.0Hz,4H),7.58(d,J＝12.0Hz,8H),7.51(s,1H),7.49–7.36(m,9H),7.34(s,1H),7.29(d,J＝8.0Hz,4H),7.25(s,1H).
Synthesis example 6 Synthesis of Compound A20:
in a single flask, 100mmol of 9- (phenyl) anthracene and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M1.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd is 2 (dba) 3 The amount of (C) added was 1mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 2-fluoro-5-chlorobenzoic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-5-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M5, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6.
Into a reaction flask were charged 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is finished,and the reaction was cooled to room temperature, water was added, filtration and washing were carried out, and the obtained solid was purified by recrystallization from toluene to obtain white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
In a single flask, 100mmol of M7 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M8.
Into a reaction flask were charged 100mmol of M8, 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a20. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M8.
1 H NMR(400MHz,Chloroform)δ8.13–8.00(m,3H),7.90(s,1H),7.82–7.69(m,3H),7.67–7.52(m,7H),7.48(d,J＝7.2Hz,4H),7.44(t,J＝10.0Hz,6H),7.34(s,1H),7.25(d,J＝7.6Hz,5H),1.69(s,6H).
Synthesis example 7 Synthesis of Compound A21:
into a reaction flask were charged 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The addition amount of (C) is 1mol% of 2-fluoro-4-chlorobenzeneboronic acid。
Into the reaction flask were charged 100mmol of M1, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2.
In a single flask, 100mmol of M2 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M3.
Into a reaction flask were charged 100mmol of M3, 100mmol of 2-pyridineboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of M4, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M4.
Into a reaction flask were charged 100mmol of 3-bromo-5-chloroiodobenzene, 100mmol of 3-pyridineboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6. Wherein Pd (PP)h 3 ) 4 The amount of the catalyst to be added was 1mol% of 3-bromo-5-chloroiodobenzene.
Into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
Into a reaction flask were charged 100mmol of M7, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a21. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M7.
1 H NMR(400MHz,Chloroform)9.24(s,1H),8.70(s,1H),8.49–8.30(m,4H),8.18(s,1H),7.87(d,J＝10.0Hz,4H),7.63–7.50(m,6H),7.50(s,2H),7.42(d,J＝7.6Hz,4H),7.14-6.90(m,7H).
Synthesis example 8 Synthesis of Compound A23
Into a reaction flask were charged 100mmol of 9-anthraceneboronic acid, 100mmol of deuterated bromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 9-anthraceneboronic acid.
In a single flask, 100mmol of 9- (1-naphthyl) anthracene and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1 hour at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of M5, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M5.
Into a reaction flask were charged 100mmol of 2-fluoro-4-chlorobenzoic acid, 100mmol of 2-iodo-3-mercaptobromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water,the solid obtained was purified by recrystallization from toluene after filtration and washing with water to obtain white powder M6. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-4-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M6, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7.
Into a reaction flask were charged 100mmol of M7, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M8. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M7.
Into a reaction flask were charged 100mmol of M5, 100mmol of M8, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a23. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
1 H NMR(400MHz,Chloroform)8.39(s,1H),8.24(d,J＝8.0Hz,2H),8.19(d,J＝10.0Hz,3H),7.96(d,J＝8.0Hz,4H),7.79-7.53(m,8H),7.45(dd,J＝10.0,8.0Hz,4H),7.25(s,1H).
Synthesis example 9 Synthesis of Compound A25
In a single flask, 100mmol of 2-phenyl-9- (1-naphthyl) anthracene and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of N-bromosuccinimide (NBS) was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M1.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd is 2 (dba) 3 The amount of (C) added was 1mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 3-fluoro-5-chloro-2-pyridineboronic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is completed, cooling the reactant to room temperature, adding water, filtering, washing the obtained solid with tolueneRecrystallization purification was performed to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst to be added was 1mol% of 3-fluoro-5-chloro-2-pyridineboronic acid.
Into the reaction flask were charged 100mmol of M5, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6.
Into a reaction flask were charged 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
In a single flask, 100mmol of M7 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M8.
Into a reaction flask were charged 100mmol of M8, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a25. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)9.24(s,1H),8.99(s,1H),8.95(s,1H),8.53(d,J＝7.6Hz,2H),8.44(d,J＝12.0Hz,3H),8.26-8.07(m,3H),7.85–7.65(m,5H),7.59(d,J＝12.0Hz,4H),7.51–7.44(m,6H),7.42–7.32(m,6H),7.25(s,1H).
Synthesis example 10 Synthesis of Compound A26
Into a reaction flask were charged 100mmol of 9, 10-dibromodeuterated anthracene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The addition amount of (2) was 1mol% of 9, 10-dibromodeuterated anthracene.
Into a reaction flask were charged 100mmol of M1, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2. Wherein Pd is 2 (dba) 3 The amount of (C) added was 1mol% based on M1.
Into a reaction flask were charged 100mmol of M2, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol biborate, 41.4g of potassium carbonate (300 mmol) and 800ml of toluene, and 1mol% of tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 ) The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is completed, cooling the reactant to room temperature, adding water, filtering, washing the obtained solidRecrystallization purification from toluene gave white powder M4. Wherein Pd is 2 (dba) 3 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 2-fluoro-5-chlorobenzoic acid, 100mmol of 2, 6-dihydroxybromobenzene, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of the catalyst was 1mol% based on 2-fluoro-5-chlorobenzeneboronic acid.
Into the reaction flask were charged 100mmol of M5, 41.4g of potassium carbonate (300 mmol) and 800ml of N, N-Dimethylformamide (DMF), and reacted at 120℃for 12 hours. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6.
Into a reaction flask were charged 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
In a single flask, 100mmol of M7 and 500ml of dichloromethane were added, the temperature was lowered to 0℃and 100mmol of triethylamine was added, 100mmol of trifluoromethanesulfonic anhydride was added in portions, the reaction was continued for 1h at 0℃and the disappearance of the starting material was monitored by Thin Layer Chromatography (TLC). Water and ethyl acetate are added into the reaction liquid to extract, and the organic phase is concentrated to obtain brown solid M8.
Into a reaction flask were charged 100mmol of M8, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, and passingThe solid obtained was purified by recrystallization from toluene after filtration and washing with water to obtain white powder A26. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ7.99(s,1H),7.74(d,J＝10.0Hz,2H),7.67(d,J＝10.8Hz,3H),7.65–7.50(m,8H),7.46(d,J＝8.0Hz,4H),7.41(s,1H),7.25(s,1H).
Other compounds of the present application can be synthesized by selecting appropriate raw materials according to the concept of synthesizing the compounds A1, A7, A8, a13, a14, a20, a21, a23, a25 or a26, or by selecting any other appropriate methods and raw materials.
Example 1
Ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in an acetone-ethanol mixed solvent, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
then placing the above-mentioned glass substrate with anode in vacuum cavity, vacuumizing to less than 10 -5 In the method, a hole injection layer is vacuum-evaporated on the anode layer film, wherein the material of the hole injection layer comprises a hole injection layer material HT-11 and a p-type dopant p-1, evaporation is performed by utilizing a multi-source co-evaporation method, the evaporation rate of the hole injection layer material HT-11 is regulated to be 0.1nm/s, the evaporation rate of the p-type dopant p-1 is 3% of the evaporation rate of the hole injection layer material HT-11, and the evaporation film thickness is 10nm; the hole injection layer material HT-11 and p-type dopant p-1 are as follows:
Then, a hole transport material HT-5 was vacuum-deposited as a hole transport layer on top of the hole injection layer, wherein the deposition rate was 0.1nm/s, the deposition film thickness was 80nm, and the hole transport material HT-5 was as follows:
then, vacuum evaporation plating is carried out on the hole transmission layer, wherein the light-emitting layer comprises a main body material A1 and a fluorescent doping agent BD-1, and evaporation plating is carried out by utilizing a multi-source co-evaporation method, wherein the evaporation plating rate of the main body material A1 is regulated to be 0.1nm/s, the evaporation plating rate of the fluorescent doping agent BD-1 is 3% of the evaporation plating rate of the main body material A1, and the thickness of the evaporation plating film is 30nm; the host material A1 and the fluorescent dopant BD-1 are as follows:
then, an electron transport layer is vacuum evaporated on the light-emitting layer, wherein the electron transport material is ET-42, the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 30nm; the electron transport material ET-42 is as follows:
then, liF with the thickness of 0.5nm is vacuum evaporated on the electron transport layer to be used as an electron injection layer, wherein the evaporation rate is 0.1nm/s;
finally, an Al layer with the thickness of 150nm is vacuum evaporated on the electron injection layer to be used as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate is 0.1nm/s.
Examples 2 to 10
The same as in example 1 was conducted except that the light-emitting layer host material was replaced with A7, A8, a13, a14, a20, a21, a23, a25 or a26, respectively, in place of A1. See in particular table 1.
Comparative example 1
The procedure of example 1 was repeated except that BH-1 was used as the host material for the light-emitting layer; BH-1 is as follows:
the organic electroluminescent device prepared by the above procedure was subjected to the following performance measurement:
the driving voltage, current efficiency and life of the organic electroluminescent devices prepared in examples 1 to 10 and comparative example 1 were measured using a digital source meter and a luminance meter under the same luminance, specifically, the voltage was increased at a rate of 0.1V per second, and the luminance of the organic electroluminescent device was measured to reach 1000cd/m 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; the lifetime test of LT95 is as follows: at 1000cd/m using a luminance meter 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 950cd/m 2 Time in hours. The results are shown in Table 1.
TABLE 1 organic electroluminescent device Performance results
From table 1, it can be seen that the compounds A1, A7, A8, a13, a14, a20, a21, a23, a25 and a26 prepared by the method are used as the main materials of the luminescent layers for the organic electroluminescent device, can effectively reduce the driving voltage, improve the current efficiency, prolong the service life of the device, and are blue light main materials with good performance.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.
Claims (13)
1. A compound of formula (I):
wherein,,
Ar 1 or Ar 2 Selected from the group consisting of
R 1 -R 5 Each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted by Rc, R 1 -R 5 Can be linked to form a ring;
R 6 -R 13 each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 6 Heteroalkyl, C unsubstituted or substituted with Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted by Rc, R 6 -R 13 Can be linked to form a ring;
L 1 or L 2 Selected from the group consisting of a bond, C which is unsubstituted or substituted by Rc 6 -C 30 Arylene, C unsubstituted or substituted with Rc 3 -C 30 Heteroarylene;
m, n are selected from 0 or 1, and m+n=1;
X 1 -X 5 each independently selected from CR or N, each R is independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R can be linked to form a ring;
Y 1 -Y 5 each independently selected from CR 'or N, each R' is independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, not takenSubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R' can be linked to form a ring;
z is selected from O, S or CRaRb, ra and Rb are each independently selected from C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 30 Aryl, C unsubstituted or substituted by Rc 3 -C 30 Heteroaryl, amino unsubstituted or substituted with Rc, said Ra and said Rb being capable of being linked to form a ring;
the heteroatoms on the heteroaryl or the heteroalkyl are each independently selected from O, S or N;
the substituents Rc of each group are each independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
2. The compound according to claim 1, wherein,
Ar 1 or Ar 2 Selected from the group consisting of
R 1 -R 5 Each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted by Rc, R 1 -R 5 Can be linked to form a ring;
R 6 -R 13 each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 3 Heteroalkyl, C unsubstituted or substituted with Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted by Rc, R 6 -R 13 Adjacent to each otherCan be linked to form a ring;
L 1 or L 2 Selected from the group consisting of a bond, C which is unsubstituted or substituted by Rc 6 -C 30 Arylene, C unsubstituted or substituted with Rc 3 -C 30 Heteroarylene;
X 1 -X 5 each independently selected from CR or N, R is each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R can be linked to form a ring;
Y 1 -Y 5 each independently selected from CR 'or N, R' is each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted with Rc, adjacent R' can be linked to form a ring;
z is selected from O, S or CRaRb, ra and Rb are each independently selected from C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, C unsubstituted or substituted by Rc 6 -C 18 Aryl, C unsubstituted or substituted by Rc 3 -C 18 Heteroaryl, amino unsubstituted or substituted with Rc, said Ra and said Rb being capable of linking to form a ring.
3. The compound of claim 1, wherein R 1 -R 5 Each independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothiopheneA group, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
4. The compound of claim 1, wherein R 6 -R 13 Each independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
5. The compound of claim 1, wherein each R is independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
6. The compound of claim 1, wherein each R' is independently selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
7. The compound of claim 1, wherein L 1 Or L 2 A subunit selected from the group consisting of a bond, unsubstituted or substituted with Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole.
8. The compound of claim 1, wherein Ra, rb are each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
9. The compound of claim 1, wherein the compound is selected from the compounds shown in A1 to a30 below:
10. an organic light-emitting material comprising at least one of the compounds of any one of claims 1 to 9.
11. An organic electroluminescent device comprising at least one of the organic luminescent materials of claim 10.
12. The organic electroluminescent device of claim 11, wherein the organic luminescent material is used as a blue host material.
13. A display device comprising the organic electroluminescent device as claimed in claim 11 or 12.
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