CN111848339A - Fluorene-containing compound, hole injection material, OLED device and preparation method and application thereof - Google Patents
Fluorene-containing compound, hole injection material, OLED device and preparation method and application thereof Download PDFInfo
- Publication number
- CN111848339A CN111848339A CN201910365325.2A CN201910365325A CN111848339A CN 111848339 A CN111848339 A CN 111848339A CN 201910365325 A CN201910365325 A CN 201910365325A CN 111848339 A CN111848339 A CN 111848339A
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- China
- Prior art keywords
- fluorene
- substituted
- containing compound
- compound
- hole injection
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 103
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002347 injection Methods 0.000 title claims abstract description 46
- 239000007924 injection Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 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 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- -1 dicyanovinyl Chemical group 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- POXIZPBFFUKMEQ-UHFFFAOYSA-N 2-cyanoethenylideneazanide Chemical group [N-]=C=[C+]C#N POXIZPBFFUKMEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 239000011737 fluorine Chemical group 0.000 claims 1
- 230000005525 hole transport Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 8
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 150000008282 halocarbons Chemical group 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004402 ultra-violet photoelectron spectroscopy Methods 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KYPOHTVBFVELTG-UHFFFAOYSA-N but-2-enedinitrile Chemical group N#CC=CC#N KYPOHTVBFVELTG-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
- C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/52—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of six-membered aromatic rings being part of condensed ring systems
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
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- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/285—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having unsaturation outside the six-membered aromatic rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/625—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing at least one aromatic ring having 7 or more carbon atoms, e.g. azulene
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a fluorene-containing compound, a hole injection material, an OLED device, a preparation method and application thereof, wherein the structure of the fluorene-containing compound is shown as a formula I; the fluorene-containing compound provided by the invention has good cross hyperconjugation characteristics and thermal stability, does not need to add extra substances, is very suitable for being used as a hole injection material of an organic electroluminescent device, can endow the material with good film-forming performance, can also endow the compound molecule with stronger reduction potential by modifying on a fluorene ring and combining with a strong electron-absorbing group, further improves the hole injection effect of the compound, assists a hole transport layer of the device to efficiently inject holes, and has good application prospect.
Description
Technical Field
The invention belongs to the field of semiconductor materials, and relates to a fluorene-containing compound, a hole injection material, an OLED device, and a preparation method and application thereof.
Background
Energy level matching is crucial for organic electroluminescent devices, and a stack structure of the organic electroluminescent device, such as a classical organic electroluminescent device, includes: the cathode, the electron transport layer, the light emitting layer, the hole transport layer and the anode are made of ITO, but the work function is high, and the energy level difference from most hole transport materials is about 0.4 eV. Therefore, if a hole injection layer is added between the anode and the hole transport layer, on one hand, the injection of charges can be increased, and on the other hand, the overall efficiency and the service life of the device can be improved.
Of course, doping some strong oxidant into the hole transport layer as a hole injection layer is also another way to improve the hole injection efficiency of the organic electroluminescent device. However, this method requires energy levels of a host material and a dopant material, and generally, the HOMO level of the host material needs to be close to the LUMO level of the guest material, so that electrons in the HOMO level can jump to the LUMO level of the dopant, and a free hole is formed in the hole transport layer, thereby increasing the conductivity of the device. Meanwhile, the doping can bend the interface energy band, and holes can be injected in a tunneling mode. For the selection of the dopant, lewis acid type metal complexes, halogens, allenes and quinones are common, and the metal complexes and the halogens have the defects of instability and the like during device processing. The allyl compounds have more steps in the synthesis and higher cost.
CN106458840A discloses a fluoroalkyl fluorene derivative, and specifically discloses a structure containing 2, 7-disubstituted 9, 9-fluoroalkyl fluorene diradical, which is shown as follows:
the R groups are the same and are selected from the group consisting of: straight or branched achiral C 1-C14Alkyl radical, C1-C14Haloalkyl, C1-C14Fluoroalkyl radical, C2-C14An alkenyl group, optionally 1, 2, 3, 4 or 5 CH therein2The group is replaced by oxygen, provided that no acetal, ketal, peroxide, or vinyl ether is present in the R group; the disclosed compounds show effective electrochemical stability and reversibility and good fluorescence lifetime when used as electroluminescent devices, but do not show strong thermal stability.
At present, compounds with spirofluorene, bifluorene and bifluorene structures are also widely applied to organic electroluminescent devices, and can be used as electron transport materials, hole injection materials and the like, and compounds with different structures show different performances.
CN102442938A discloses a novel compound, which has stable properties, simple preparation process, high luminous efficiency and high carrier mobility, and can be used in the electron transport layer of electroluminescent devices. The applied device can obviously reduce the driving voltage and improve the current efficiency. The compound mother nucleus is selected from 2, 10-disubstituted-7, 7,14, 14-tetraalkyl-7, 14-dihydrofluoreno [2,1a ] fluorene, and the structure is shown as follows:
the terminal groups Ar1 and Ar2 are selected from pyridine groups, phenyl groups, biphenyl groups or naphthyl groups, A, B is a chemical bond or an aromatic ring with 6-30 carbon atoms, R is an alkyl group with 1-12 carbon atoms or an aryl group with 6-30 carbon atoms, and m and n are integers of 0-2. The pyridine groups lacking electrons are introduced to two sides of the fluoreno [2,1a ] fluorene group, so that the charge transfer capability of the compound can be improved, and the compound has good electron transfer performance. Meanwhile, the aromatic group connected with the pyridyl can improve the molecular weight of the compound so as to increase the glass transition temperature of the compound; it is also possible to reduce the coplanarity of such compounds and thus to improve their film-forming properties. Has higher stability at room temperature, and the applied device also has higher stability. However, this compound has a complicated structure and is not suitable for use in an electron transport layer as a material for a hole injection layer.
The existing hole injection material usually can be doped with metal complexes, strong oxidants and the like, has the problems of instability in processing, has higher requirements on the energy level of the material, is expensive and has higher cost, and is not beneficial to actual production and application. How to develop a material which has good stability and hole injection property during processing is of great significance for its application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a fluorene-containing compound, a hole injection material, an OLED device, a preparation method and an application thereof, so as to solve the problems of poor hole injection capability caused by high cost and high LUMO energy level due to unstable heat during processing and additional doping of other substances in the existing material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a fluorene-containing compound, wherein the structure of the compound is shown in formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Independently selected from any one of hydrogen, halogen atom, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted aryloxy;
X1And X2Independently selected from any one of alkylene or substituted alkylene.
According to the fluorene-containing compound provided by the invention, the fluorenyl groups are connected at the positions 4 and 5 of the fluorenyl groups, so that the molecular weight of the compound is increased, a carbon-based framework is formed, the thermal stability of the compound is enhanced, and compared with the single fluorenyl group which has the problem of small molecular weight and thermal instability, the fluorene-containing compound has better thermal stability; meanwhile, a double bond is introduced to the 9-position of the fluorenyl group to form a large cross-conjugation system together with the two fluorenyl groups, so that the compound has good cross-hyperconjugation characteristic and lower LUMO energy level, the stability of the compound is further improved, the compound is very suitable for being used as a hole injection material of an organic electroluminescent device, and the material can be endowed with good film-forming performance.
The halogen atom in the invention includes any one of fluorine atom, chlorine atom or bromine atom.
The alkyl in the invention can be straight-chain alkyl or branched-chain alkyl, and can be alkyl with chirality or alkyl without chirality. More specifically methyl, ethyl, n-propyl, isopropyl, n-heptyl, octadecyl, eicosyl and the like, and generally, an achiral alkyl group is preferred. The alkylene group in the present invention may be a linear alkylene group or a branched alkylene group, and specifically may be a methylene group, an ethylene group, or the like; the substituted alkylene group may be substituted with any group, and may be, for example, cyanomethylene, dicyanomethylene, or the like 
And the dotted line indicates the position of the double bond access in formula I.
The alkoxy group in the present invention may be a linear alkoxy group or a branched alkoxy group, and may be, for example, a methoxy group, an ethoxy group, an isopropoxy group, or the like.
The alkenyl group in the present invention may be vinyl, propenyl, 1, 3-butadienyl, etc., and the substituted alkenyl group may be cyanovinyl, dicyanovinyl, etc.
The aryl groups described herein may be phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, and the like; heteroaryl groups can be pyridyl, pyrrolyl, thienyl, furyl, indolyl, quinolinyl, and the like; the aryloxy group may be phenoxy, naphthoxy, or the like.
The substitution in the present invention means that alkyl, aryl and the like groups can be substituted with any substituent, wherein the substituent can be halogen atom, cyano, alkynyl, aryl, heteroaryl, aryloxy, halogenated hydrocarbon group, alkenyl or cyano-substituted alkenyl, sulfonic group, amino and the like; more preferred is a cyano group, a halogenated hydrocarbon group, a halogen atom or a cyano-substituted alkenyl group; wherein the halogenated hydrocarbon group may be a trifluoromethyl group, a chloropropyl group or the like.
Preferably, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Independently selected from any one of halogen atom, cyano, substituted alkyl, alkenyl, substituted alkenyl, aryl or substituted aryl.
Preferably, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Independently selected from any one of fluorine atom, cyano, trifluoromethyl, vinyl, dicyanovinyl, phenyl, fluorenyl or trifluoromethyl substituted phenyl.
Preferably, X1And X2Independently selected from any one of alkylene, fluoro-substituted alkylene or cyano-substituted alkylene.
Preferably, X1And X2Independently selected from any one of methylene, difluoromethylene or dicyanomethylene.
In the present invention, the substituent of the fluorene ring mainly affects the hole injection effect of the compound, and secondly, has a certain effect on the thermal stability of the compound. Substituents on the fluorene ring, i.e. in formula I, R1～R12And X1、X2Can be totally substituted, partially substituted orThe substituent groups are the same or different, and the substituent groups can be uniformly substituted or randomly substituted.
The total substitution, partial substitution and non-substitution on the fluorene ring have an influence on the properties of the compound, and the total substitution has a better hole injection effect than the partial substitution and non-substitution.
The substituent on the fluorene ring is preferably a strong electron-withdrawing group, such as a cyano group, dicyanoethylene, fluoro group, trifluoromethyl group, and the like, and due to the strong electron-withdrawing property of these groups, a strong reduction potential can be imparted to the molecule, and the hole injection effect can be further improved, thereby assisting the hole transport layer to efficiently perform hole injection.
If a substituent on the fluorene ring is a group which does not have strong electron absorption property, such as alkyl, the LUMO level of the material is increased after the compound is prepared into the material, and the hole injection performance of the material is seriously affected.
In addition, the substituents on the fluorene ring are generally not selected to be relatively reactive groups. For example, when the substituent on the fluorene ring is a chlorine atom, it is reactive and easily generates radicals, which ultimately affects the device performance.
The fluorene-containing compound includes
Any one of them.
Preferably, the fluorene-containing compound is
Any one of them.
In the present invention, the fluorene-containing compounds are preferred to have better thermal stability and hole injection effect.
In a second aspect, the present invention provides a preparation method of the fluorene-containing compound according to the first aspect, the preparation method including a coupling reaction of a compound a and a compound b under the catalysis of a palladium catalyst to obtain the fluorene-containing compound, wherein the structure of the compound a is
The structure of the compound b is
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12And X1And X2In the same manner as defined in the first aspect, i.e., R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Independently selected from any one of hydrogen, halogen atom, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted aryloxy; x 1And X2Independently selected from any one of alkylene or substituted alkylene.
Preferably, the molar ratio of the compound a to the compound b is 1: 1-1.2, and may be 1:1, 1:1.05, 1:1, 1:1.12, 1:1.15, 1:1.18 or 1:1.2, for example.
Preferably, the palladium catalyst comprises tetrakis (triphenylphosphine) palladium and/or palladium acetate.
The palladium catalyst of the present invention is not limited to the above-mentioned compounds, and any divalent palladium compound which can be catalyzed can be used in the reaction of the present invention.
Preferably, the amount of the palladium catalyst is 0.1 to 5% of the compound a, for example, 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, etc. calculated by mole.
Preferably, the coupling reaction is carried out in the presence of magnesium.
Preferably, the molar ratio of the compound a to magnesium is 1: 1.1-1.5, and may be, for example, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5, etc.
Preferably, the solvent of the coupling reaction is diethyl ether and/or tetrahydrofuran.
Preferably, the coupling reaction is carried out under protection of a protective gas.
Preferably, the protective gas comprises any one of nitrogen, neon or argon or a combination of at least two thereof.
Preferably, the temperature of the coupling reaction is 30 to 100 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
Preferably, the coupling reaction time is 20-100 h, for example, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h or 100 h.
In a third aspect, the present invention provides a hole injection material comprising the fluorene-containing compound according to the first aspect.
The fluorene-containing compound provided by the invention has good thermal stability and hole injection performance, so the prepared hole injection material has good hole injection efficiency,
in a fourth aspect, the present invention provides an OLED device whose hole injection layer comprises a hole injection material as described in the third aspect.
In a fifth aspect, the present invention provides the fluorene-containing compound of the first aspect, the hole injection material of the third aspect, and the use of the OLED device of the fourth aspect in the preparation of a semiconductor device.
Compared with the prior art, the invention has the following beneficial effects:
the fluorene group is connected to the 4 and 5 positions of the fluorene group, so that the molecular weight of the compound is increased, a carbon-based framework is formed, the thermal stability of the compound is enhanced, the compound is generally not affected at more than 400 ℃, the highest temperature can reach 500-600 ℃, and compared with the single fluorene group, the compound has smaller molecular weight and has the problem of thermal instability; meanwhile, a double bond is introduced to the 9 position of the fluorenyl group to form a large cross conjugation system together with the two fluorenyl groups, so that the compound has good cross super conjugation property and lower LUMO energy level, the LUMO value can reach-5.2-5.5 eV generally, the stability of the compound is further improved, no additional substance is required to be added, the compound is very suitable for being used as a hole injection material of an organic electroluminescent device, and the material can be endowed with good film-forming property.
According to the fluorene-containing compound provided by the invention, the fluorene ring is modified, and a strong electron-absorbing group is combined, so that a strong reduction potential can be given to the compound molecules, the hole injection effect of the compound is further improved, and the hole injection is efficiently carried out by a hole transport layer of an auxiliary device.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw materials, solvents, catalysts and the like for the reactions used in the examples of the present invention can be purchased directly or synthesized according to known methods.
The thermogravimetric analyzer used in the embodiment of the present invention has the following model: TGA/DSC 1/1100SF of METTLER.
Example 1
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, a-1(49.84g,112.8mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (3.1g,127.5mmol), tetrakis (triphenylphosphine) palladium (288.9mg,0.25mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product a-2.
MS：568.31。
13C-NMR：(2C,101.3),(4C,118.5),(4C,147.8),(4C,135.4),(4C,149.3),(4C,132.0),(2C,148.3),(4C,119.6)。
Example 2
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, b-1(54.8g,112.7mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (3.1g,127.5mmol), tetrakis (triphenylphosphine) palladium (288.9mg,0.25mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product b-2.
MS：652.54。
13C-NMR：(2C,101.3),(2C,148.3),(4C,142.8),(12C,116.5),(4C,113.8),(4C,118.8),(4C,115.3),(4C,138.9),(4C,143.9)。
Example 3
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, c-1(54.8g,69.0mmol), anhydrous tetrahydrofuran (300 mL), magnesium turnings (1.8g,75.3mmol), and palladium acetate (56.1mg,0.25mmol) were added under argon protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using 100mL of petroleum ether (60-90 ℃) for three times, washing with saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product c-2.
MS：1268.44；
13C-NMR：(2C,67.1),(4C,117.2),(2C,176.7),(4C,134.7),(4C,107.3),(4C,125.2),(4C,123.9),(4C,107.0),(4C,126.7),(4C,106.8),(4C,137.1),(4C,135.8)。
Example 4
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, d-1(52.2g,108.8mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (2.9g,119.8mmol), tetrakis (triphenylphosphine) palladium (288.9mg,0.25mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product d-2.
MS：640.27。
13C-NMR：(2C,156.1),(2C,79.7),(4C,118.5),(4C,147.8),(4C,135.4),(4C,149.3),(4C,132.0),(4C,119.6)。
Example 5
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, e-1(25.2g,75mmol), e-2(33.3g,75mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (3.9g,163.4mmol), tetrakis (triphenylphosphine) palladium (520mg,0.45mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product e-3.
MS：460.37。
13C-NMR：(2C,101.3),(2C,148.3),(4C,134.3),(4C,125.6),(4C,127.8),(2C,127.1),(2C,149.3),(2C,132.0),(2C,133.2),(2C,135.4),(2C,119.6)。
Example 6
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, f-1(50.1g,134.7mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (3.5g,142.8mmol), tetrakis (triphenylphosphine) palladium (358.2mg,0.31mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product f-2.
MS：424.39。
13C-NMR：(2C,101.3),(2C,148.3),(4C,121.3),(4C,159.2),(4C,114.8),(4C,128.7),(4C,134.8),(4C,131.0)。
Example 7
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, g-1(40.1g,119.3mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (3.1g,125.8mmol), tetrakis (triphenylphosphine) palladium (358.2mg,0.31mmol) were added under argon protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product g-2.
MS：352.43。
13C-NMR：(2C,101.3),(2C,148.3),(4C,134.3),(4C,125.6),(4C,127.8),(4C,127.1),(4C,135.4),(4C,133.2)。
Example 8
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, h-1(43.1g,102.6mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (2.8g,115.8mmol), tetrakis (triphenylphosphine) palladium (358.2mg,0.31mmol) were added under argon protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using 100mL of petroleum ether (60-90 ℃) for three times, washing with saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product h-2.
MS：520.75。
13C-NMR：(2C,101.3),(2C,148.3),(4C,131.9),(4C,8.9),(4C,135.4),(4C,138.4),(4C,8.6),(4C,136.9),(4C,8.4),(4C,133.0),(4C,130.0)。
Example 9
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, j-1(49.4g,105.1mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (2.7g,111.3mmol), tetrakis (triphenylphosphine) palladium (358.2mg,0.31mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product j-2.
MS：620.39。
13C-NMR：(2C,116.3),(2C,136.9),(2C,114.9),(2C,141.3),(4C,118.5),(4C,147.8),(4C,135.4),(4C,149.3),(4C,119.6),(4C,132.0)。
Example 10
This example provides a fluorene-containing compound having the following specific reaction formula:
to a 500mL dry three-necked flask, k-1(59.8g,93.4mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (2.5g,105.1mmol), tetrakis (triphenylphosphine) palladium (358.2mg,0.31mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing by using saturated salt water to be neutral, combining organic phases, drying overnight by using anhydrous magnesium sulfate, carrying out suction filtration and concentration to obtain a colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product k-2.
MS：961.19。
13C-NMR：(24C,127.4),(16,129.0),(8C,136.6),(8C,132.6),(4C,137.7),(8C,134.8),(4C,133.7),(2C,148.3),(2C,101.3)。
Comparative example 1
The comparative example provides a compound of
Comparative example 2
This comparative example provides a fluorene-containing compound having the specific reaction formula:
to a 500mL dry three-necked flask, l-1(45.4g,105.1mmol), anhydrous tetrahydrofuran 300mL, magnesium turnings (2.5g,105.1mmol), tetrakis (triphenylphosphine) palladium (337.8mg,0.29mmol) were added under nitrogen protection, and the oil bath was warmed to 80 ℃ and refluxed for two days. And after the reaction product is cooled to room temperature, extracting by using petroleum ether (60-90 ℃) for 100mL for three times, washing with saturated salt water to be neutral, combining organic phases, drying over night by anhydrous magnesium sulfate, performing suction filtration and concentration to obtain colorless liquid, and then passing through a 200-300-mesh silica gel column to obtain a colorless product l-2.
The OLED device provided by the invention is prepared by the following method:
and ultrasonically cleaning the transparent anode electrode ITO substrate in isopropanol for 10min, exposing the transparent anode electrode ITO substrate to ultraviolet light for 30min, and treating the transparent anode electrode ITO substrate with plasma for 10 min. And then putting the processed ITO substrate into evaporation equipment. First, a layer of 50nm NPB and a compound (the fluorene-containing compound provided in examples 1 to 10, the molar ratio of the fluorene-containing compound to the NPB being 1:33.3) were mixed and evaporated as a hole injection layer, and then, a layer of 30nm NPB was evaporated on the mixed layer
As hole transport layer, mixed evaporation of CBP
And 5% of Ir (ppy)3 
A film thickness of 30nm as a green light emitting layer, followed by vapor deposition of Alq of 30nm3(8-Hydroxyquinolinylaluminum
Then, the organic light-emitting diode is used as an electron transport layer, then, LiF with the thickness of 2nm is evaporated to be used as an electron injection layer, and finally, metal Al with the thickness of 150nm is evaporated to form a metal cathode to manufacture an OLED device (organic light-emitting element).
The fluorene-containing compounds provided in examples 1 to 10 and comparative examples 1 to 2 described above were subjected to a hole injection performance test (LUMO level test step: energy gap Eg of the material obtained by a UV-visible light tester (Eg 1240/band edge absorption); HOMO level of the material obtained by Ultraviolet Photoelectron Spectroscopy (UPS); LUMO value calculated from the relationship between HOMO, LUMO and Eg, specifically: LUMO ═ HOMO + Eg) and a thermal stability test (TGA test step: sample mass 2 to 5mg, test temperature range 50 to 600 ℃, temperature rise rate: 10 ℃/min, taking a weight loss of 0.5% to represent thermal stability of the material).
The specific results obtained are shown in table 1.
TABLE 1
| Sample (I) | Hole injection property (ev) | Thermal stability (. degree. C.) |
| Example 1 | -5.3 | 413 |
| Example 2 | -5.5 | 432 |
| Example 3 | -5.3 | 569 |
| Example 4 | -5.3 | 416 |
| Example 5 | -5.2 | 402 |
| Example 6 | -5.2 | 395 |
| Example 7 | -4.8 | 399 |
| Example 8 | -4.9 | 407 |
| Example 9 | -5.3 | 428 |
| Example 10 | -4.9 | 486 |
| Comparative example 1 | -5.0 | 343 |
| Comparative example 2 | -5.3 | 406 |
The conclusions that can be made by the analysis of the data in table 1 are:
from the comparison of example 1 with examples 5, 6 and 7, it is understood that when the fluorenyl group contains more electron-withdrawing groups such as fluorine atoms, the hole injection property and thermal stability of the compound are higher. Further, the more the substituents are, the better the hole injecting property of the compound is exhibited.
From the comparison between example 1 and example 8, it is clear that if the electron-withdrawing group is not strong on the fluorenyl group, the compound has poor hole injection property although it still has good thermal stability.
From a comparison between example 1 and example 10, it is clear that the compound has a poor hole injection property, although it has a good thermal stability when benzene is used as a substituent.
As is clear from a comparison between example 1 and comparative example 1, the thermal stability of the compound was very poor when the fluorenyl group alone was used.
As is clear from the comparison between example 1 and comparative example 2, the double bond at the 9-position of the fluorenyl group greatly improves the thermal stability of the compound.
As described above, the fluorene-containing compound provided by the present invention has both excellent thermal stability and hole injection property.
The applicant states that the present invention is illustrated by the above examples of the fluorene-containing compound, the hole injection material, the OLED device and the methods of making and using the same, but the present invention is not limited to the above detailed methods, i.e. it does not mean that the present invention must be implemented by relying on the above detailed methods. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A fluorene-containing compound is characterized in that the structure of the fluorene-containing compound is shown as a formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Independently selected from any one of hydrogen, halogen atom, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted aryloxy;
X1and X2Independently selected from any one of alkylene or substituted alkylene.
2. The fluorene-containing compound of claim 1, wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Independently selected from any one of halogen atom, cyano, substituted alkyl, alkenyl, substituted alkenyl, aryl or substituted aryl;
preferably, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Independently selected from any one of fluorine atom, cyano, trifluoromethyl, vinyl, dicyanovinyl, phenyl, fluorenyl or trifluoromethyl substituted phenyl.
3. The fluorene-containing compound according to claim 1 or 2, wherein X is1And X2Independently selected from any one of alkylene, fluorine substituted alkylene or cyano substituted alkylene;
preferably, X1And X2Independently selected from any one of methylene, difluoromethylene or dicyanomethylene.
4. The fluorene-containing compound according to any one of claims 1 to 3, wherein the fluorene-containing compound comprises
Any one of the above;
preferably, the fluorene-containing compound is
Any one of them.
5. The method for preparing a fluorene-containing compound according to any one of claims 1 to 4, wherein the method comprises a coupling reaction of a compound a and a compound b under the catalysis of a palladium catalyst to obtain the fluorene-containing compound, wherein the structure of the compound a is 
The structure of the compound b is
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12And X1And X2The same as defined in claim 1.
6. The preparation method according to claim 5, wherein the molar ratio of the compound a to the compound b is 1: 1-1.2;
preferably, the palladium catalyst comprises tetrakis (triphenylphosphine) palladium and/or palladium acetate;
preferably, the amount of the palladium catalyst is 0.1-5% of that of the compound a calculated by molar amount;
preferably, the coupling reaction is carried out in the presence of magnesium;
preferably, the molar ratio of the compound a to magnesium is 1: 1.1-1.5.
7. The process according to claim 5 or 6, wherein the solvent for the coupling reaction is diethyl ether and/or tetrahydrofuran;
preferably, the coupling reaction is carried out under the protection of protective gas;
preferably, the protective gas comprises any one of nitrogen, neon or argon or a combination of at least two thereof;
preferably, the temperature of the coupling reaction is 30-100 ℃;
preferably, the coupling reaction time is 20-100 h.
8. A hole injection material comprising the fluorene-containing compound according to any one of claims 1 to 4.
9. An OLED device, characterized in that the hole injection layer of the OLED device comprises the hole injection material according to claim 8.
10. Use of a fluorene-containing compound according to any one of claims 1-4, a hole injection material according to claim 8, an OLED device according to claim 9 for the manufacture of a semiconductor device.
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