CN116283909A - Organic electronic transmission material and preparation method and application thereof - Google Patents
Organic electronic transmission material and preparation method and application thereof Download PDFInfo
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- CN116283909A CN116283909A CN202310547015.9A CN202310547015A CN116283909A CN 116283909 A CN116283909 A CN 116283909A CN 202310547015 A CN202310547015 A CN 202310547015A CN 116283909 A CN116283909 A CN 116283909A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000005540 biological transmission Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 35
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims description 48
- -1 cyano, methyl Chemical group 0.000 claims description 45
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 125000001624 naphthyl group Chemical group 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004305 biphenyl Chemical group 0.000 claims description 14
- 235000010290 biphenyl Nutrition 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000004076 pyridyl group Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 125000005561 phenanthryl group Chemical group 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical group C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 7
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 7
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-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
- 239000003513 alkali Substances 0.000 claims description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 4
- 125000005870 benzindolyl group Chemical group 0.000 claims description 4
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 claims description 4
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 claims description 4
- 125000005874 benzothiadiazolyl group Chemical group 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 4
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000001041 indolyl group Chemical group 0.000 claims description 4
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 125000001725 pyrenyl group Chemical group 0.000 claims description 4
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 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 3
- 125000003828 azulenyl group Chemical group 0.000 claims description 3
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 3
- 125000003838 furazanyl group Chemical group 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 3
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001715 oxadiazolyl group Chemical group 0.000 claims description 3
- 125000002971 oxazolyl group Chemical group 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 claims description 3
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 3
- 125000001113 thiadiazolyl group Chemical group 0.000 claims description 3
- 125000000335 thiazolyl group Chemical group 0.000 claims description 3
- 125000004306 triazinyl group Chemical group 0.000 claims description 3
- 125000001425 triazolyl group Chemical group 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-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
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-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
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- BVCRYZCZHIUGTH-UHFFFAOYSA-N triazine-4-carbonitrile Chemical compound N#CC1=CC=NN=N1 BVCRYZCZHIUGTH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 10
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 60
- 230000000052 comparative effect Effects 0.000 description 33
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 239000000543 intermediate Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 230000005525 hole transport Effects 0.000 description 8
- BKQXUNGELBDWLS-UHFFFAOYSA-N 9,9-diphenylfluorene Chemical group C1=CC=CC=C1C1(C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 BKQXUNGELBDWLS-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- FMKGJQHNYMWDFJ-CVEARBPZSA-N 2-[[4-(2,2-difluoropropoxy)pyrimidin-5-yl]methylamino]-4-[[(1R,4S)-4-hydroxy-3,3-dimethylcyclohexyl]amino]pyrimidine-5-carbonitrile Chemical compound FC(COC1=NC=NC=C1CNC1=NC=C(C(=N1)N[C@H]1CC([C@H](CC1)O)(C)C)C#N)(C)F FMKGJQHNYMWDFJ-CVEARBPZSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229940127113 compound 57 Drugs 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229940126639 Compound 33 Drugs 0.000 description 3
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical group N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- JJPWJEGNCRGGGA-UHFFFAOYSA-N 4-[[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]amino]benzoic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)NC1=CC=C(C(=O)O)C=C1 JJPWJEGNCRGGGA-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/549—Organic PV cells
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Abstract
The invention provides an organic electronic transmission material, a preparation method and application thereof, and a structural general formula is shown in the specification. The organic electron transport material provided by the invention has sp at 9 positions of fluorene ring 3 The hybridized carbon maintains the spatial configuration of the compound; the bridged substituted heteroaryl enables the compound to have electron-withdrawing property, is favorable for electron transmission, enhances the recombination of electrons and holes in the light-emitting layer, and thus improves the light-emitting efficiency of the device; by heteroaryl groups differing in phenyl or naphthylThe position is replaced to further avoid the occurrence of large planes in the molecule to enhance the interaction between molecules, so that the service life of the device is shortened; meanwhile, the heteroaryl groups are bridged at different positions of the 9-position benzene ring of fluorene, so that the reduction of electron transmission caused by bipolar molecular property can be avoided. In particular, the present invention has developed an electron transport material having high mobility, so that the OLED prepared therefrom has the performance advantages of high luminous efficiency and long life.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic electronic transmission material and a preparation method and application thereof.
Background
Compared with the traditional display and illumination technology, the organic light-emitting diode (OLED) has obvious advantages such as no need of a backlight source, light weight, low energy consumption, high response speed, flexibility, clearness in displaying moving images, no smear and the like, and can meet the performance requirements of people on an information display system in multiple aspects.
The OLED specifically includes electrode material layers and organic functional materials sandwiched between different electrode layers, including a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). The ETL layer is a key component in the OLED structure and is responsible for adjusting the injection speed and injection quantity of electrons, but the electron mobility of the common organic material is lower, the hole mobility is higher, and the unbalance of electrons and holes in the device is caused, so that the efficiency and the stability of the device are reduced.
In recent years, although research on organic electron transport materials has been conducted more, development of an electron transport material having high mobility so that an OLED prepared therefrom has performance advantages of high luminous efficiency and long life has been a problem that a person skilled in the art is urgently required to solve.
Disclosure of Invention
In view of the above, the present invention provides an organic electron transport material and a method for preparing the same, which are capable of providing an OLED having high luminous efficiency and long life by developing an electron transport material having high mobility.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an organic electron transport material having a structure represented by formula I:
i is a kind of
Wherein, the liquid crystal display device comprises a liquid crystal display device,
Z 1 ~Z 3 independently represent C, N atoms, Z 1 ~Z 3 Wherein the number of N is 2 or 3;
Z 4 ~Z 9 independently represent C, N atoms, Z 4 ~Z 9 Wherein N numbers are integers of 0-3;
r is independently selected from hydrogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C24 aryl, and substituted or unsubstituted C3-C24 heteroaryl;
a is an integer of 1 to 5;
and when Z is 4 ~Z 9 When the two are C atoms, R has at least one strong electron withdrawing group, and is selected from cyano, triazine, triazole, pyridazine, pyrimidine, pyrazine, imidazole, oxazole, thiazole, pyrazole, pyridine, benzimidazole, benzothiazole and quinoline;
R 1 represents a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C6-C24 aryl group, or a substituted or unsubstituted C3-C24 heteroaryl group;
m, n independently represent integers of 0, 1, 2;
Ar 1 ，Ar 2 independently represents a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C3-C24 heteroaryl group.
Further, R is selected from cyano;
r is selected from substituted or unsubstituted C1-C6 alkyl, preferably methyl, ethyl, n-propyl and isopropyl;
R，Ar 1 ，Ar 2 when selected from substituted or unsubstituted C6-C24 aryl groups, phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, dimethylfluorenyl, benzofluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, naphtonaphthyl, fluoranthenyl, azulenyl, 9-dimethylfluorenyl, phenanthryl, and combinations thereof are preferred;
R，Ar 1 ，Ar 2 when selected from substituted or unsubstituted C3 to C24 heteroaryl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, carbazolyl, and benzocarbazolyl are preferred.
R 1 When selected from substituted or unsubstituted C1-C3 alkyl, methyl and ethyl are preferred;
R 1 when selected from substituted or unsubstituted C6 to C24 aryl, phenyl, naphthyl and biphenyl are preferred;
R 1 when selected from substituted or unsubstituted C3 to C24 heteroaryl, pyridinyl, pyrazinyl, pyrimidinyl and pyridazinyl are preferred.
Further, Z 1 ~Z 3 Are all N;
r represents cyano, methyl, phenyl, biphenyl, naphthyl, anthracenyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl;
R 1 represented by methyl, phenyl, biphenyl, naphthyl;
m, n independently represent 0 or 1;
Ar 1 ，Ar 2 independently represents phenyl, biphenyl, naphthyl, dibenzofuranyl, carbazolyl, 9-dimethylfluorenyl, phenanthryl, and combinations thereof.
Further, R represents cyano, methyl, phenyl, pyridinyl;
Ar 1 ，Ar 2 independently represents phenyl, biphenyl, naphthyl;
the general formula I includes the following structure:
in the above-mentioned technical scheme, the method comprises the steps of,
the substitution positions are defined as follows:
the term "substituted or unsubstituted" refers to the number of carbon atoms of a substituent that make up the unsubstituted number of carbon atoms, regardless of the number of carbon atoms in the substituent.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, fluorenyl, dimethylfluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, furanyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, carbazolyl, benzocarbazolyl, or a substituent linked by two or more of the substituents indicated above, or not.
Aryl refers to monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems, polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings being "fused");
heteroaryl groups include monocyclic aromatic groups and polycyclic aromatic ring systems of at least one heteroatom including, but not limited to O, S, N, P, B, si and Se;
the compounds specifically have the following structure, but are not limited thereto:
synthetic route
1）N 2 Under the protection, adding reactant 1 (1.0 eq), reactant 2 (1.3-1.5 eq), palladium catalyst (0.01-0.02 eq) and alkali (2.0-2.3 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, heating to 80-100 ℃, reacting for 8-10h, cooling to room temperature, adding water, filtering after solid precipitation is finished, drying a filter cake, purifying the rest substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the intermediate 1.
2）N 2 Under the protection, adding the intermediate 1 (1.0 eq), the reactant 3 (1.0-1.2 eq), the palladium catalyst (0.01-0.02 eq) and the alkali (2.0-2.3 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, heating to 80-100 ℃, reacting for 8-12h, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the formula I.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
reactant 1 and reactant 3 can be obtained from known starting materials or synthesized by:
under the protection of nitrogen, the reactant b (1.0 eq), the reactant a (1.5-1.8 eq), the palladium catalyst (0.05-0.1 eq) and the potassium acetate (2.0-3.0 eq) are dissolved in N, N-Dimethylformamide (DMF), the temperature is raised to 85-95 ℃, the reaction is carried out for 8-12h, and a rotary evaporator is used for removing the solvent. Adding dichloromethane into the residue, stirring, filtering, and purifying the residual substances by using column chromatography to obtain a reactant 1;
reactant 3 was synthesized by the method of synthesizing reactant 1, and reactant a was replaced with reactant c.
Hal is selected from Cl, br; hal1 is selected from Br, I;
r' is
Or->
；
A is boric acid or pinacol ester of biboric acid;
R、R 1 、Ar 1 ~Ar 2 、Z 1 ~Z 3 、Z 4 ~Z 9 and m, n have the definitions given above.
Further, the palladium catalyst may be: pd (Pd) 2 (dba) 3 ，Pd(PPh 3 ) 4 ，PdCl 2 ，PdCl 2 (dppf)，Pd(OAc) 2 ，Pd(PPh 3 ) 2 Cl 2 ，NiCl 2 (dppf)；
The base may be: k (K) 2 CO 3 ，K 3 PO 4 ，Na 2 CO 3 ，CsF，Cs 2 CO 3 ，t-BuONa。
In the invention, two halogens exist in the synthesis of the intermediate 1 and the reactant 1, according to the characteristic that the reactivity I > Br > Cl in the palladium catalytic coupling reaction, the reaction site is controlled by controlling the reaction condition to prepare the intermediate, and the by-product is removed by column chromatography or silica gel funnel purification reaction, so as to obtain the target compound. The following are referred to in the common general knowledge:
transition metal organic chemistry (original sixth edition), robert H-Crabtree (Robert H. Crabtree), press: publication time of Shanghai Shandong university Press: 2017-09-00, ISBN:978-7-5628-5111-0, page 388.
Organic chemistry and photoelectric Material Experimental Instructions, chen Runfeng, press: university of east south Press, publication time: 2019-11-00, ISBN:9787564184230, page 174.
The invention also discloses application of the organic electronic transmission material in preparing organic electroluminescent devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an organic electron transport material, wherein one substituent at 9-position of fluorene in the compound is benzene substituted by naphthyl, and the other substituent is R of the invention 1 The radicals shown are, at the same time, the phenyl ring and the naphthyl radical being attached to the heteroaryl radical directly or via phenylene, respectively. The OLED device prepared from the electron transport material provided by the invention has good comprehensive performance, and particularly has obvious improvement effect on the service life and luminous efficiency of the device.
In the present invention, sp at 9-position of fluorene ring 3 The hybrid carbon can keep the spatial configuration of the compound, and avoid poor film forming property and short service life of the device caused by molecular stacking; the heteroaryl is introduced to enable the compound to have the property of electron attraction, thereby being beneficial to electron transmission and enhancing the recombination of electrons and holes in the luminescent layer, and further improving the luminescent efficiency of the device; bridging heteroaryl groups at different positions of the 9-benzene ring of fluorene can avoid weakening electron transmission caused by bipolar molecules (which are beneficial to hole transmission and electron transmission); simultaneously, the heteroaryl is substituted at different positions of the phenyl or the naphthyl, so that the occurrence of a large plane in a molecule can be further avoided, the interaction between molecules is weakened, and the service life of the device is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediates 1-165 in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 165 in example 1.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of compound 196 in example 2.
Fig. 4 is a nuclear magnetic resonance hydrogen spectrum of compound 393 of example 3.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of compound 416 in example 4.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: synthesis of Compound 165
Under nitrogen, reactant b-165 (20 mmol), reactant a-165 (30 mmol, CAS: 1432909-93-7), pd (PPh 3 ) 4 (1 mmol) and potassium acetate (40 mmol) were dissolved in DMF, warmed to 90℃and reacted for 8h, and the solvent was removed using a rotary evaporator. Adding dichloromethane into the residue, stirring, filtering, and purifying the rest material by column chromatography to obtain reactants 1-165;
N 2 under protection, reactants 1-165 (20 mmol), reactants 2-165 (30 mmol, CAS: 73207-97-3), pd (PPh) 3 ) 4 (0.2 mmol) and K 2 CO 3 (40 mmol) are added into a mixed solvent of toluene, ethanol and water (3:1:1) respectively, the temperature is raised to 85 ℃, the reaction is carried out for 8 hours, the temperature is cooled to room temperature, water is added, after the solid is separated out, the filtration is carried out, a filter cake is dried, the residual substances are purified by a column chromatography, the solvent is removed from the filtrate by a rotary evaporator, and the obtained solid is dried, thus obtaining the intermediate 1-165. (5.00 g, yield: 56%, test value MS (ESI, M/Z): [ M+H ]] + = 445.98, mass spectrometer model Waters XEVO TQD, low precision, test with ESI source);
the nuclear magnetic resonance hydrogen spectra of intermediates 1-165 are shown in FIG. 1:
N 2 under protection, intermediate 1-165 (20 mmol), reactant 3-165 (22 mmol, CAS: 248624-48-7), pd (PPh) 3 ) 4 （0.2mmol）、K 2 CO 3 (40 mmol) was added to a mixed solvent of toluene, ethanol, and water (3:1:1), the temperature was raised to 90℃for 10 hours, the reaction was cooled to room temperature, water was added, filtration was performed after completion of precipitation of the solid, the cake was dried, the remaining material was purified by column chromatography, the solvent was removed from the filtrate by a rotary evaporator, and the obtained solid was dried to give compound 165 (11.79 g, yield: 64%, test value MS (ESI, M/Z): [ M+H] + = 921.19）；
The nuclear magnetic resonance hydrogen spectrum of compound 165 is shown in fig. 2:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 87.46, H, 4.93, N, 7.61
Test value: c, 87.38, H, 5.02, N, 7.65
Example 2: synthesis of Compound 196
Synthesizing a compound 196 according to the method for synthesizing the compound 165, and replacing reactants a-165 and reactants 3-165 with reactants a-196 and reactants 3-196;
the reaction gave compound 196 at 11.05g, yield: 61%, test value MS (ESI, M/Z) [ M+H ]] + = 906.15）；
The nmr hydrogen spectrum of compound 196 is shown in fig. 3:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.91, H, 4.90, N, 6.19
Test value: c, 88.82, H, 4.98, N, 6.23.
Example 3: synthesis of Compound 393
Under nitrogen, reactant b-165 (20 mmol), reactant c-393 (25 mmol), pd (PPh) 3 ) 4 (1 mmol) and potassium acetate (40 mmol) were dissolved in DMF, warmed to 90℃and reacted for 8h, and the solvent was removed using a rotary evaporator. Adding dichloromethane into the residue, stirring, filtering, and purifying the residual material by column chromatography to obtain reactant 3-393;
N 2 under protection, reactants 1-393 (20 mmol), reactants 2-393 (22 mmol), pd (PPh) 3 ) 4 （0.2eq）、K 2 CO 3 (40 mmol) respectively adding into a mixed solvent of toluene, ethanol and water (3:1:1), heating to 90 ℃, reacting for 10 hours, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the rest substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate 1-393;
synthesizing a compound 393 according to the method for synthesizing the intermediate 1-393, and respectively replacing reactants 1-393 and reactants 2-393 with reactants 3-393 and the intermediate 1-393;
the reaction gave compound 393 at 9.98g, yield: 63, test value MS (ESI, M/Z) [ M+H ]] + = 792.01）；
The nmr hydrogen spectrum of compound 393 is shown in fig. 4:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.07, H, 4.84, N, 7.08
Test value: c, 87.98, H, 4.93, N, 7.13.
Example 4: synthesis of Compound 416
Synthesizing an intermediate 1-416 according to the method for synthesizing the intermediate 1-393, and replacing reactants 1-393 with reactants 1-196;
synthesizing the compound 416 according to the method for synthesizing the intermediate 1-393, and replacing the reactants 1-393 and the reactants 2-393 with the reactants 3-416 and the intermediate 1-416 respectively;
the reaction gave compound 416 as 9.96g, yield: 59, test value MS (ESI, M/Z) [ M+H ]] + = 844.08）；
The nmr hydrogen spectrum of compound 416 is shown in fig. 5:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.33, H, 5.02, N, 6.65
Test value: c, 88.21, H, 5.11, N, 6.71.
Examples 5 to 55
The synthesis of the following compounds, whose molecular formulas and mass spectra are shown in Table 1 below, was accomplished with reference to the synthesis methods of examples 1-4.
Table 1 molecular formula and mass spectrum
| Examples | Compounds of formula (I) | Molecular formula | Mass spectrometry test values |
| Example 5 | 1 | C 62 H 42 N 4 | 844.08 |
| Example 6 | 17 | C 50 H 34 N 4 | 691.89 |
| Example 7 | 23 | C 50 H 34 N 4 | 691.91 |
| Example 8 | 27 | C 56 H 38 N 4 | 768.00 |
| Example 9 | 33 | C 67 H 44 N 4 | 906.17 |
| Example 10 | 56 | C 61 H 40 N 4 | 830.16 |
| Example 11 | 57 | C 55 H 36 N 4 | 753.97 |
| Example 12 | 62 | C 55 H 36 N 4 | 753.96 |
| Example 13 | 64 | C 55 H 36 N 4 | 753.97 |
| Example 14 | 70 | C 50 H 34 N 4 | 691.90 |
| Example 15 | 74 | C 50 H 34 N 4 | 691.89 |
| Example 16 | 75 | C 50 H 34 N 4 | 691.90 |
| Example 17 | 76 | C 55 H 36 N 4 | 753.96 |
| Example 18 | 79 | C 55 H 36 N 4 | 753.98 |
| Example 19 | 81 | C 57 H 40 N 4 | 782.02 |
| Example 20 | 84 | C 58 H 41 N 3 | 781.01 |
| Example 21 | 92 | C 57 H 40 N 4 | 782.04 |
| Example 22 | 95 | C 57 H 40 N 4 | 782.02 |
| Example 23 | 100 | C 52 H 38 N 4 | 719.93 |
| Example 24 | 101 | C 57 H 37 N 5 | 792.99 |
| Example 25 | 107 | C 62 H 39 N 5 | 855.08 |
| Example 26 | 113 | C 61 H 41 N 5 | 845.08 |
| Example 27 | 117 | C 66 H 43 N 5 | 907.18 |
| Example 28 | 120 | C 74 H 50 N 4 | 996.29 |
| Example 29 | 131 | C 63 H 43 N 3 | 843.08 |
| Example 30 | 139 | C 68 H 46 N 4 | 920.19 |
| Example 31 | 142 | C 74 H 47 N 5 | 1007.28 |
| Example 32 | 149 | C 64 H 46 N 4 | 872.17 |
| Example 33 | 153 | C 64 H 46 N 4 | 872.15 |
| Example 34 | 158 | C 70 H 46 N 4 | 944.21 |
| Example 35 | 174 | C 69 H 45 N 5 | 945.21 |
| Example 36 | 182 | C 69 H 47 N 3 | 919.18 |
| Example 37 | 192 | C 69 H 44 N 4 | 930.17 |
| Example 38 | 201 | C 64 H 39 N 5 | 879.13 |
| Example 39 | 212 | C 67 H 42 N 4 O | 920.16 |
| Example 40 | 234 | C 56 H 38 N 4 | 768.00 |
| Example 41 | 248 | C 63 H 44 N 4 | 858.11 |
| Example 42 | 249 | C 64 H 42 N 4 | 868.11 |
| Example 43 | 263 | C 68 H 44 N 4 | 918.16 |
| Example 44 | 270 | C 68 H 44 N 4 O | 934.17 |
| Example 45 | 278 | C 71 H 47 N 5 | 971.25 |
| Example 46 | 283 | C 72 H 49 N 5 | 985.29 |
| Example 47 | 298 | C 67 H 44 N 4 O | 922.16 |
| Example 48 | 303 | C 69 H 48 N 4 | 934.21 |
| Example 49 | 320 | C 73 H 44 N 4 O 2 | 1010.22 |
| Example 50 | 339 | C 64 H 45 N 3 | 866.12 |
| Example 51 | 348 | C 68 H 45 N 3 | 905.16 |
| Example 52 | 368 | C 69 H 45 N 5 | 945.22 |
| Example 53 | 377 | C 57 H 39 N 3 | 766.99 |
| Example 54 | 388 | C 67 H 44 N 4 | 906.17 |
| Example 55 | 392 | C 68 H 46 N 4 | 920.18 |
Further, since other compounds of the present invention can be obtained by referring to the synthetic methods of the above-mentioned examples, they are not exemplified herein.
The invention provides an organic electroluminescent device, which specifically can comprise a hole injection layer, a hole transmission layer, an electron blocking layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transmission layer, an electron injection layer, a cap layer and the like as structures of organic layers. In one embodiment, the organic light emitting element may be described as an "organic layer" disposed between the cathode and the anode, which may be achieved by combining the above layers, or some layers may be omitted or added entirely.
According to one embodiment of the present specification, the compound of formula I prepared according to the present invention is used as an electron transport layer material.
The anode is made of a conductor such as a metal, metal oxide, and/or conductive polymer that has a higher work function to aid in hole injection. The metal can be nickel, platinum, vanadium, chromium, copper, zinc, gold, silver or alloys thereof; the metal oxide can be zinc oxide, indium Tin Oxide (ITO) or indium zinc oxide; the combination of metal and oxide can be ZnO and A1 or SnO 2 Sb or ITO and Ag; the conductive polymer may be selected from poly (3-methylthiophene), poly (3, 4- (ethylene-1, 2-dioxy) thiophene), polypyrrole, and polyaniline, but is not limited thereto.
The hole injection layer and the hole transport layer efficiently inject or transport holes from the anode between the electrodes to which an electric field has been applied, and preferably have high hole injection efficiency and efficiently transport the injected holes. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and which is less likely to cause impurities that become traps during production and use, is preferable. The hole injection layer is preferably a p-doped hole injection layer; the hole transport material may be selected from arylamine derivatives, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like.
A light-emitting auxiliary layer (multi-layer hole transporting layer) is interposed between the hole transporting layer and the light-emitting layer, and functions to smoothly move holes from the anode to the light-emitting layer and block electrons from the cathode.
The light-emitting layer is preferably a compound which emits light by excitation by recombination of holes and electrons, and is preferably a compound which can form a stable thin film shape and exhibits high light-emitting efficiency in a solid state. The light emitting layer may be a single layer or multiple layers and may include a host material and a dopant material. The amounts of the host material and the dopant material to be used may be determined in accordance with the respective material characteristics. The doping method may be realized by co-evaporation with the host material, or may be formed by simultaneous evaporation after mixing with the host material.
The electron transport layer and the electron injection layer efficiently transport or inject electrons from the anode and cathode between the electrodes to which an electric field has been applied. An impurity substance which has a large electron affinity, a large electron mobility, and excellent stability and is not likely to cause a trap is preferable.
The anode is a substance capable of injecting electrons with good efficiency, and the same material as that of the anode can be selected. If a low work function metal is chosen that facilitates efficient electron injection, it is often necessary to dope trace amounts of lithium, cesium or magnesium to avoid its instability in the atmosphere.
There are no particular restrictions on the other layer materials in an OLED device, except that the electron transport layer disclosed in the present invention comprises formula I.
The organic electron transport material and the organic electroluminescent device according to the present invention will be described in detail with reference to specific examples.
Application example 1 preparation of organic electroluminescent device:
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, washing with distilled water for 2 times repeatedly, washing with ultrasonic waves for 10min, baking with a vacuum oven at 220 ℃ for 2 hours after washing, and cooling after baking is finished, so that the glass substrate can be used. The substrate is used as an anode, a vapor deposition device process is performed by using a vapor deposition machine, and other functional layers are sequentially vapor deposited on the substrate.
b. HIL (hole injection layer): vacuum evaporation of hole injection layer materials HT and P-dopant at an evaporation rate of 1 Å/s, wherein the ratio of the evaporation rates of HT and P-dopant is 97:3, the thickness is 10nm.
c. HTL (hole transport layer): HT of 120nm was vacuum deposited as a hole transport layer on top of the hole injection layer at a deposition rate of 1.5 Å/s.
d. Prime (light-emitting auxiliary layer): a 10nm prime is vacuum deposited on the hole transport layer as a light emitting auxiliary layer at a deposition rate of 0.5 Å/s.
e. EML (light emitting layer): then, on the above light-emitting auxiliary layer, a Host material (Host) and a Dopant material (Dopant) having a thickness of 25nm were vacuum-evaporated as light-emitting layers at an evaporation rate of 1 Å/s, wherein the ratio of the evaporation rates of Host and Dopant was 97:3.
f. HB (hole blocking layer): a hole blocking layer having a thickness of 5.0nm was vacuum deposited at a deposition rate of 0.5. 0.5 Å/s.
g. ETL (electron transport layer): compound 165 and Liq, which were 35nm thick, were vacuum evaporated as electron transport layers at an evaporation rate of 1 Å/s. Wherein the evaporation rate ratio of compound 165 to Liq is 50:50.
h. EIL (electron injection layer): an electron injection layer was formed by vapor deposition of 1.0nm on a Yb film layer at a vapor deposition rate of 0.5. 0.5 Å/s.
i. And (3) cathode: and evaporating magnesium and silver at 18nm at an evaporation rate ratio of 1 Å/s, wherein the evaporation rate ratio is 1:9, so as to obtain the OLED device.
j. Light extraction layer: CPL with a thickness of 70nm was vacuum deposited as a light extraction layer on the cathode at a deposition rate of 1 Å/s.
k. And packaging the substrate subjected to evaporation. Firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
The device structure is as follows:
ITO/Ag/ITO/HT P-dose (10 nm)/HT (120 nm)/prime (10 nm)/Host (dose (25 nm)/HB (5 nm)/ET (compound of the invention): liq (35 nm)/Yb (1 nm)/Mg: ag (18 nm)/CPL (70 nm).
The structural formula of the compound in the device is as follows:
application examples 2 to 55
The organic electroluminescent devices of application examples 2 to 55 were prepared according to the above-described preparation method of the organic electroluminescent device, except that the compound 165 of application example 1 was replaced with the corresponding compound of examples 2 to 55, respectively, to form an electron transport layer.
Device comparative examples 1-8:
the organic electroluminescent devices of comparative examples 1 to 8 were prepared according to the above-described preparation method of the organic electroluminescent device, except that the compound 165 of application example 1 was replaced with the comparative compounds 1 to 8, respectively, to form an electron transport layer. Wherein, the structural formula of the comparative compounds 1-8 is as follows:
the organic electroluminescent devices obtained in the above device examples 1 to 55 and device comparative examples 1 to 8 were characterized in terms of driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
TABLE 2 luminescence property test results (brightness value 1000 nits)
Note that: bi=light emission efficiency/CIEy in table 2, the light emission efficiency is affected by chromaticity in the blue OLED device.
As can be seen from table 2, the OLED devices prepared using the organic electron transport materials provided in the examples of the present invention were superior in terms of lifetime of devices in the application examples 1 to 55 compared with the conventional OLED devices provided in comparative examples 1 to 8, and the series structures according to the general formula of the present invention improved by 59 to 119 hours as compared with the comparative examples, and increased in light emitting efficiency by 5 to 17% as compared with the comparative examples. Meanwhile, the compounds according to the general formula of the present invention are also improved in BI value and driving voltage as compared with the comparative examples.
The specific compound structure and performance are compared as follows:
the structure of the comparative compound 1 is similar to that of the compound 57 in the example provided by the invention, the difference is that the substituted position of 9, 9-diphenyl fluorene in the comparative compound 1 is a benzene ring part in a fluorene ring, the substituted position of 9, 9-diphenyl fluorene in the compound 57 is a phenyl group at the 9 position, and further, the comparison shows that the benzene ring part in the fluorene ring of the comparative compound 1 is bonded with 2-naphthyl, and the compound 57 is bonded with 2-pyridyl on the benzene ring at the 9 position of the fluorene ring. Because naphthyl belongs to electron-rich substituent groups, pyridyl is electron-deficient substituent groups, the bipolar property of the comparative compound 1 is obvious, namely the capability of transporting holes and electrons is equivalent; compound 57 appears to be more electron deficient and is more conducive to electron transport. In addition, the mobility of the organic hole transport material is generally two orders of magnitude higher than that of the organic hole transport material, so that the compound 57 provided by the invention is used as an electron transport material to be more favorable for the recombination of holes and electrons, thereby improving the device efficiency, and as can be seen from Table 2, the luminous efficiency of the compound 57 is improved by 0.85cd/A compared with that of the comparative compound 1.
Among them, the structure of the comparative compound 2 is similar to that of the compound 234 in the example provided by the invention, wherein the comparative compound 2 has a1, 4-phenylene group which plays a role in connection in structure, and the compound 234 has a1, 5-naphthylene group, wherein the 1, 4-phenylene group forms a plane with a phenyl group and a biphenyl group substituted triazine part, and the latter has a structure twisted due to substitution on different rings of the naphthyl group, and the 1, 5-naphthyl group is not in the same plane with the phenyl group and the biphenyl group substituted triazine part. Therefore, the compound 234 provided by the invention can avoid the defects of easy stacking, easy aggregation and poor fluidity of molecules caused by a large plane in the molecule in the comparative compound 2, thereby prolonging the service life of the device, and the data in the table 2 shows that the service life of the compound 234 is prolonged by 106h compared with that of the comparative compound 2, and in addition, the compound 234 is more beneficial to electron transmission due to the fact that the electron-withdrawing 3-pyridyl group is introduced into the compound 234, so that the efficiency of the device is also enhanced by 0.72cd/A. Similarly, the 337 structure provided by the invention is also significantly improved in terms of device lifetime and luminous efficiency over comparative compound 3.
Wherein, the structure of the comparative compound 4 is similar to that of the compound 368 in the examples provided by the invention, the 3-phenyl-9, 9-dimethylfluorenyl and 2, 4-diphenyl-1, 3, 5-triazinyl are bridged by 3,3'-1,1' -diphenyl in the comparative compound 4, and the 2, 4-diphenyl-1, 3, 5-triazinyl and other groups are bridged by 1, 7-naphthyl and 3,3'-1,1' -diphenyl in the comparative compound 368. The position of biphenyl group in the comparison compound is a diagonal position, so that the space three-dimensional property of the structure is poor, the compound 368 enhances the torsion of the configuration by introducing 1, 7-naphthyl, reduces the defects of poor film forming property and short service life of a device caused by molecular aggregation and crystallization, and simultaneously, the compound 368 introduces a strong electron-withdrawing group 2-cyano-4-phenylpyridyl, so that the electron transmission performance is obviously enhanced. As can be seen from Table 2, the lifetime of compound 368 is increased by 101h, and the luminous efficiency is improved by 0.74cd/A.
Wherein, comparing the structure of the comparative compound 5 with that of the compound 192 in the embodiment provided by the invention, the 4-position of 9, 9-diphenyl fluorene is substituted in the comparative compound 5, and the meta position of the same 9-position phenyl of 9, 9-diphenyl fluorene in the compound 192 is substituted by a group, so that the molecular structure is twisted, the intermolecular interaction force is weakened, and the service life of the device is prolonged by 90 hours relative to that of the comparative compound 5.
The structure of the compound 278 in the comparative compound 6 is similar to that of the compound 278 in the embodiment provided by the invention, but the 9, 10-anthrylene group and the bonded spirobifluorene group in the comparative compound 6 perform better in the aspect of hole transmission, so that the compound 278 has bipolar property, the bonding of the 9, 9-diphenyl fluorene 9-position phenyl group and the 3-cyanopyridine group in the meta position of the 9-benzene ring are bonded, and the electron-withdrawing characteristic of pyridine and cyano group makes the electron transmission property of the whole compound 278 stronger than that of the compound 6, so that the hole and electron recombination is facilitated, the device efficiency is improved, and the service life of the device is prolonged.
The structure of the comparative compound 7 is similar to that of the compound 33 in the embodiment provided by the invention, but the present invention is substituted on the same benzene ring at 9 position of 9, 9-diphenyl fluorene, and the comparative compound 7 is substituted on two benzene rings at 9 position respectively, so that the structural symmetry is better than that of the compound 33, thereby leading to easy stacking of molecules and reducing the service life of the device, and compared with the comparative compound 7, the service life of the compound 33 is improved by 73h as shown in table 2.
The structure of the comparative compound 8 is similar to that of the compound 56 in the embodiment provided by the invention, but the substitution is carried out on the same benzene ring at the 9 position of 9, 9-diphenyl fluorene, and the comparative compound 8 is respectively substituted on two benzene rings at the 9 position, so that the structural symmetry of the compound is better than that of the compound 56, the molecules are easy to stack, the service life of the device is reduced, and the service life of the device is reduced by 100h compared with that of the compound 56. In addition, the structure in which only phenylene-naphthyl-phenyl is introduced into the benzene ring at the 9-position in the comparative compound 8, and the electron withdrawing group is not present, so that the whole molecule has poor electron transmission, the driving voltage is increased by 0.08V relative to the compound 56, and the efficiency is reduced by 0.47cd/A.
In conclusion, the sp of the 9 position of the fluorene ring of the organic electronic transmission material provided by the invention 3 The hybridized carbon maintains the spatial configuration of the compound; the bridged substituted heteroaryl enables the compound to have electron-withdrawing property, is favorable for electron transmission, enhances the recombination of electrons and holes in the light-emitting layer, and thus improves the light-emitting efficiency of the device; substitution of heteroaryl at different positions of phenyl or naphthyl further avoids the occurrence of large planes in the molecule to enhance intermolecular interactions, resulting in shortened device lifetime; meanwhile, the heteroaryl groups are bridged at different positions of the 9-benzene ring of fluorene, so that the reduction of electron transmission caused by bipolar molecular arrangement can be avoidedWeak.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. An organic electron transport material characterized by having a structure represented by formula I:
i is a kind of
Wherein, the liquid crystal display device comprises a liquid crystal display device,
Z 1 ~Z 3 independently represent C, N atoms, Z 1 ~Z 3 Wherein the number of N is 2 or 3;
Z 4 ~Z 9 independently represent C, N atoms, Z 4 ~Z 9 Wherein N numbers are integers of 0-3;
r is independently selected from hydrogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C24 aryl, and substituted or unsubstituted C3-C24 heteroaryl;
a is an integer of 1 to 5;
and when Z is 4 ~Z 9 When the two are C atoms, R has at least one strong electron withdrawing group, and is selected from cyano, triazine, triazole, pyridazine, pyrimidine, pyrazine, imidazole, oxazole, thiazole, pyrazole, pyridine, benzimidazole, benzothiazole and quinoline;
R 1 represents a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C6-C24 aryl group, or a substituted or unsubstituted C3-C24 heteroaryl group;
m, n independently represent integers of 0, 1, 2;
Ar 1 ，Ar 2 independently represents a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C3-C24 heteroaryl group.
2. The organic electronic transmission material according to claim 1, wherein R is selected from cyano, methyl, ethyl, n-propyl, isopropyl, phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, dimethylfluorenyl, benzofluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, naphtofrenyl, fluoranthenyl, azulenyl; furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, carbazolyl, benzocarbazolyl, and 9, 9-dimethylfluorenyl, phenanthryl, and combinations thereof;
Ar 1 ，Ar 2 selected from phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, dimethylfluorenyl, benzofluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, naphtonenaphthyl, fluoranthenyl, azulenyl; furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolineA group, a quinazolinyl group, a carbazolyl group, a benzocarbazolyl group, and a 9, 9-dimethylfluorenyl group, a phenanthryl group, and combinations thereof;
R 1 selected from the group consisting of methyl, ethyl, phenyl, naphthyl, biphenyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl.
3. The organic electron transport material according to claim 2, wherein Z 1 ~Z 3 Are all N;
r represents cyano, methyl, phenyl, biphenyl, naphthyl, anthracenyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl;
R 1 represented by methyl, phenyl, biphenyl, naphthyl;
m, n independently represent 0 or 1;
Ar 1 ，Ar 2 independently represents phenyl, biphenyl, naphthyl, dibenzofuranyl, carbazolyl, 9-dimethylfluorenyl, phenanthryl, and combinations thereof.
4. An organic electron transport material according to claim 3, wherein R represents cyano, methyl, phenyl, pyridinyl;
Ar 1 ，Ar 2 independently represents phenyl, biphenyl, naphthyl;
the general formula I includes the following structure:
5. the organic electron transport material according to claim 1, wherein the organic electron transport material is selected from any one of the compounds represented by the following structural formulas:
6. a method for preparing an organic electron transport material according to any one of claims 1 to 5, comprising the steps of:
（1）N 2 under the protection, respectively adding reactant 1 (1.0 eq), reactant 2 (1.3-1.5 eq), palladium catalyst (0.01-0.02 eq) and alkali (2.0-2.3 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1), heating to 80-100 ℃, reacting for 8-10h, cooling to room temperature, adding water, and standing for solidsFiltering after precipitation, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate 1;
（2）N 2 under the protection, respectively adding the intermediate 1 (1.0 eq), the reactant 3 (1.0-1.2 eq), the palladium catalyst (0.01-0.02 eq) and the alkali (2.0-2.3 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1), heating to 80-100 ℃, reacting for 8-12h, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the formula I;
the specific synthetic route is as follows:
wherein reactant 1 and reactant 3 can be obtained from known starting materials or synthesized by:
under the protection of nitrogen, dissolving a reactant b (1.0 eq), a reactant a (1.5-1.8 eq), a palladium catalyst (0.05-0.1 eq) and potassium acetate (2.0-3.0 eq) in N, N-Dimethylformamide (DMF), heating to 85-95 ℃, reacting for 8-12h, removing a solvent by using a rotary evaporator, adding dichloromethane into residues, stirring, filtering, and purifying the residual substances by using a column chromatography to obtain a reactant 1;
synthesizing a reactant 3 according to the method for synthesizing the reactant 1, and replacing the reactant a with a reactant c to obtain the catalyst;
hal is selected from Cl, br; hal1 is selected from Br, I;
r' is
Or->
；
A is boric acid or pinacol ester of biboric acid;
R、R 1 、Ar 1 ~Ar 2 、Z 1 ~Z 3 、Z 4 ~Z 9 and m, n have the definitions given in claim 1.
7. The method for producing an organic electron transport material according to claim 6, wherein the palladium catalyst is selected from Pd 2 (dba) 3 ，Pd(PPh 3 ) 4 ，PdCl 2 ，PdCl 2 (dppf)，Pd(OAc) 2 ，Pd(PPh 3 ) 2 Cl 2 ，NiCl 2 (dppf); the base is selected from K 2 CO 3 ，K 3 PO 4 ，Na 2 CO 3 ，CsF，Cs 2 CO 3 ，t-BuONa。
8. Use of an electron transport material according to any of claims 1 to 5 or prepared by a method according to any of claims 6 to 7 for the preparation of an organic electroluminescent device.
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| CN117486817A (en) * | 2024-01-02 | 2024-02-02 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and preparation method and application thereof |
| CN117486817B (en) * | 2024-01-02 | 2024-05-28 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and preparation method and application thereof |
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| CN115745977A (en) * | 2023-01-10 | 2023-03-07 | 吉林奥来德光电材料股份有限公司 | Electron transport material, preparation method thereof and organic electroluminescent device |
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| CN117362274A (en) * | 2023-12-07 | 2024-01-09 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material, preparation method thereof and organic electroluminescent device |
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| CN117486817A (en) * | 2024-01-02 | 2024-02-02 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and preparation method and application thereof |
| CN117486817B (en) * | 2024-01-02 | 2024-05-28 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and preparation method and application thereof |
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