CN112898199B - 一种含有氮原子杂环和苯甲腈的有机电子传输材料及其应用 - Google Patents
一种含有氮原子杂环和苯甲腈的有机电子传输材料及其应用 Download PDFInfo
- Publication number
- CN112898199B CN112898199B CN202110106379.4A CN202110106379A CN112898199B CN 112898199 B CN112898199 B CN 112898199B CN 202110106379 A CN202110106379 A CN 202110106379A CN 112898199 B CN112898199 B CN 112898199B
- Authority
- CN
- China
- Prior art keywords
- organic
- electron transport
- compound
- benzonitrile
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 6
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- -1 9,9-dimethylfluorenyl Chemical group 0.000 claims description 19
- 239000012044 organic layer Substances 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 230000005669 field effect Effects 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 108091008695 photoreceptors Proteins 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 239000012776 electronic material Substances 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 93
- 150000001875 compounds Chemical class 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 230000032258 transport Effects 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 14
- 239000012065 filter cake Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000000921 elemental analysis Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 8
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940126543 compound 14 Drugs 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- AVYVHIKSFXVDBG-UHFFFAOYSA-N N-benzyl-N-hydroxy-2,2-dimethylbutanamide Chemical compound C(C1=CC=CC=C1)N(C(C(CC)(C)C)=O)O AVYVHIKSFXVDBG-UHFFFAOYSA-N 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- BJXYHBKEQFQVES-NWDGAFQWSA-N enpatoran Chemical compound N[C@H]1CN(C[C@H](C1)C(F)(F)F)C1=C2C=CC=NC2=C(C=C1)C#N BJXYHBKEQFQVES-NWDGAFQWSA-N 0.000 description 4
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YJLIKUSWRSEPSM-WGQQHEPDSA-N (2r,3r,4s,5r)-2-[6-amino-8-[(4-phenylphenyl)methylamino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CNC1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O YJLIKUSWRSEPSM-WGQQHEPDSA-N 0.000 description 3
- OBSBUDOCBMVAMN-UHFFFAOYSA-N 10-bromo-2-chlorophenanthrene Chemical compound BrC1=CC2=CC=CC=C2C=2C=CC(=CC1=2)Cl OBSBUDOCBMVAMN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- JWOJBRHCHHNBBH-UHFFFAOYSA-N ClC(C=C1)=CC2=C1C1=CC=CC=C1C(Br)=C2 Chemical compound ClC(C=C1)=CC2=C1C1=CC=CC=C1C(Br)=C2 JWOJBRHCHHNBBH-UHFFFAOYSA-N 0.000 description 3
- POFVJRKJJBFPII-UHFFFAOYSA-N N-cyclopentyl-5-[2-[[5-[(4-ethylpiperazin-1-yl)methyl]pyridin-2-yl]amino]-5-fluoropyrimidin-4-yl]-4-methyl-1,3-thiazol-2-amine Chemical compound C1(CCCC1)NC=1SC(=C(N=1)C)C1=NC(=NC=C1F)NC1=NC=C(C=C1)CN1CCN(CC1)CC POFVJRKJJBFPII-UHFFFAOYSA-N 0.000 description 3
- 229940127113 compound 57 Drugs 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SNXHTSDNICSFJU-UHFFFAOYSA-N B(O)(O)O.C(#N)C=1C=C(C=CC1)CC(O)(C)C(C)(C)O Chemical compound B(O)(O)O.C(#N)C=1C=C(C=CC1)CC(O)(C)C(C)(C)O SNXHTSDNICSFJU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 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 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
- OGSKSQJAIQSTRI-UHFFFAOYSA-N 9-bromo-3-chlorophenanthrene Chemical compound ClC1=CC2=C(C=C1)C=C(Br)C1=C2C=CC=C1 OGSKSQJAIQSTRI-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- UEUJFCQTODXMIP-UHFFFAOYSA-N ClC(C=C1)=CC2=C1C(Br)=CC1=CC=CC=C21 Chemical compound ClC(C=C1)=CC2=C1C(Br)=CC1=CC=CC=C21 UEUJFCQTODXMIP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 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
- 125000005104 aryl silyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D213/24—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 with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/57—Nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- 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
- C07D405/02—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 two hetero rings
- C07D405/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明涉及有机电致发光技术领域，具体涉及一种含有氮原子杂环和苯甲腈的有机电子材料及其应用。其结构通式如式I所示，
Ar1和Ar2为取代或者未取代的C6‑C30的芳基，取代或者未取代的C3‑C30的杂芳基中的一种；Z1、Z2和Z3中至少有一个为N，其它为CH；R为氢、氘、氟、氰基、三氟甲基、甲基、乙基、异丙基、丙基中的一种。
Description
技术领域：
本发明涉及有机电致发光技术领域，具体涉及一种含有氮原子杂环和苯甲腈的有机电子材料及其应用。
背景技术：
有机电致发光器件(OLEDs)作为一种新型的显示技术，每个像素切换自如且主动发光，具有响应时间短，色彩对比度高；驱动电压低等优点；有机材料的使用使得器件更加轻薄，环保；有机电致发光器件已经广泛应用在手机、平板显示器、电视、照明和车载显示等领域。
一般的有机电致发光器件采用夹层式三明治结构，即有机层夹在两侧阳极和阴极之间，有机层按照各种材料不同的光电特性分为空穴传输层、电子传输层、发光层、空穴阻挡层和电子阻挡层等。器件的发光机理主要为：在外界电压驱动下，空穴和电子克服能垒，分别由阳极和阴极注入到空穴传输层和电子传输层，然后在发光层中复合并释放能量，并把能量传递给有机发光物质。发光物质得到能量，并使其从基态跃迁到激发态，当受激发分子重新跃迁到基态，就产生了发光现象。
电子传输材料就是把阴极上的电子传输到发光层的材料。电子传输材料一般要求较好的热稳定性和成膜性，较高的电子迁移率、较大的电子亲和能和较高的激发态能级。常用的电子传输材料有三(8-羟基喹啉)铝(Alq3)，TPBI，BCP，Bphen等，最近的有机电致发光器件尽管已经得到逐渐改良，但仍要求在发光效率，驱动电压，寿命等方面更为优异的材料，因此，需要开发具有良好热稳定性和性能优良的电子传输材料。
发明内容：
本发明正是针对上述问题，提供了一种含有氮原子杂环和苯甲腈的有机电子传输材料及其应用。本发明引入苯甲腈基、三嗪等氮原子基团，同时用大共轭体系的菲基作为桥链，增强材料电负性的同时，也增加材料的共轭体系，提高化合物的电子传输性能和材料的热稳性。同时利用具有高热稳定性、成膜性，及强电子迁移率的有机电致发光化合物制备具有优异的发光效率，器件寿命更长的有机电致发光器件。
为了实现上述目的，本发明采用如下技术方案，其结构通式如式(I)所示，
Ar1和Ar2为取代或者未取代的C6-C30的芳基，取代或者未取代的C3-C30的杂芳基中的一种；
Z1、Z2和Z3中至少有一个为N，其它为CH；
R为氢、氘、氟、氰基、三氟甲基、甲基、乙基、异丙基、丙基中的一种；
R1-R8中至少有一个为苯甲腈基，其他的为氢，氘，卤素，取代或未取代的C1-C20的烷基，取代或者未取代的C6-C30的芳基，取代或取代的具有C1-C20的烷氧基，取代或未取代的具有C6-C30的芳氧基，取代或未取代的具有2～20个碳原子的烯基，取代或未取代的具有C3-C30的杂芳基，取代或未取代的具有C3-C20的烷硅基，取代或未取代的具有C6-C20的芳基硅烷基，胺基，酰基，羰基，羧酸基，酯基，腈，异腈，硫基，亚磺酰基，磺酰基，膦基中的一种。
优选地，Ar1和Ar2为苯基，甲苯基，联苯基，萘基，菲基，蒽基，苝基，苯基萘基，萘基苯基，二苯基苯基，9,9-二甲基芴基，9,9-二苯基芴基，9,9-螺二芴基，荧蒽基，二苯并呋喃基，二苯并噻吩基，苯并菲基，苯基二苯并呋喃基，咔唑基中的一种。
优选地，R为氢，甲基，氘，氰基中的一种。
R1-R8中至少有一个为苯甲腈基，其他的为氢，氘，甲基，苯基，吡啶基中的一种。
具体地，本发明所述的有机电子材料包括并不限于以下化合物1-144中的任意一种，
所述的有机电子材料可被用于生产有机电致发光器件、有机太阳能电池、有机薄膜晶体管、有机光检测器、有机场效应晶体管、有机集成电路和有机光感受器。
有机电致发光器件包括阳极、阴极和有机层，有机层包含发光层、空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层以上，有机层中至少有一层含有上述的有机电子材料。
优选地，所述的有机层中发光层含有上述的有机电子材料。
优选地，所述的有机层中电子传输层或者电子注入层含有上述的有机电子材料。
优选地，所述的有机层中空穴阻挡层含有上述的有机电子材料。
优选地，所述的有机层的总厚度为1-1000nm；进一步优选地，所述的有机层的总厚度为50-500nm。
本发明的有机电致发光器件中有机层的每一层，可以通过真空蒸镀法、分子束蒸镀法、溶于溶剂的浸涂法、旋涂法、棒涂法或者喷墨打印等方式制备，对于金属电极可以使用蒸镀法或者溅射法进行制备。
本发明的有益效果：
本发明提供的有机电子传输材料具有较好热稳定性，良好的电子迁移率，制备简单等优点。采用该有机电致发光化合物制作的有机电致发光器件能够降低驱动电压、提高发光效率、色纯度优异、延长器件寿命的效果。
附图说明：
图1实施例4化合物73的质谱图。
图2实施例5化合物92的质谱图。
图3实施例8化合物133的质谱图。
图4本发明的有机电致发光器件结构示意图。
其中，110代表为玻璃基板，120代表为阳极，130代表为空穴注入层，140空穴传输层，150代表为阻挡层，160代表为发光层，170代表为电子传输层，180代表为电子注入层，190代表为阴极。
图5为实施例9-13的器件的电压与亮度关系图。
图6为实施例9-13的器件的电流密度电流效率关系图。
具体实施方式：
下面，结合附图以及具体实施方式，对本发明做进一步描述，但下述实施例仅为本发明的优选实施例，并非全部。基于实施方式中的实施例，本领域技术人员在没有做出创造性劳动的前提下所获得其它实施例，都属于本发明的保护范围。
实施例1化合物14的合成
步骤1：化合物14-1的合成
在氮气保护下，往烧瓶中加入2-氯-10-溴-菲(1.7g，5.9mmol)，2,4-二苯基-6-(4-苯基硼酸频哪酯)嘧啶(2.54g，5.9mmol)和碳酸钾(2g，15mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，四三苯基膦钯(0.05g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.6g产品，收率87％。HRMS(ESI,m/z):[M+H]+:519.1625。
步骤2：化合物14的合成
在氮气保护下，往烧瓶中加入化合物14-1(2.5g，4.8mmol)，3-氰基苯频哪醇硼酸酯(1.4g，5.8mmol)和碳酸钾(1.4g，10mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，醋酸钯(0.05g)和X-phos(0.1g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.1g产品，收率76％。元素分析：C43H27N3，C,88.16；H,4.66；N,7.18，HRMS(ESI,m/z):[M+H]+:586.2285。
实施例2化合物48的合成
步骤1：化合物48-1的合成
在氮气保护下，往烧瓶中加入3-氯-9-溴-菲(2g，6.9mmol)，2,4-二苯基-6-(4-苯基硼酸频哪酯)-1,3,5-三嗪(3g，6.9mmol)和碳酸钾(2g，15mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，四三苯基膦钯(0.05g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.9g产品，收率82％。HRMS(ESI,m/z):[M+H]+:520.1584。
步骤2：化合物48的合成
在氮气保护下，往烧瓶中加入化合物48-1(2.5g，4.8mmol)，3-氰基苯频哪醇硼酸酯(1.4g，5.8mmol)和碳酸钾(1.4g，10mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，醋酸钯(0.05g)和X-phos(0.1g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到1.9g产品，收率69％。元素分析：C42H26N4，C,85.95；H,4.48；N,9.57，HRMS(ESI,m/z):[M+H]+:587.2238。
实施例3化合物57的合成
步骤1：化合物57-1的合成
在氮气保护下，往烧瓶中加入2-氯-10-溴-菲(3g，10.3mmol)，2,4-二苯基-6-(3-苯基硼酸频哪酯)-1,3,5-三嗪(4.5g，10.3mmol)和碳酸钾(3.4g，25mmol)，再加入甲苯(30mL)，乙醇(15mL)和去离子水(15mL)，四三苯基膦钯(0.05g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到4.3g产品，收率71％。HRMS(ESI,m/z):[M+H]+:520.1583。
步骤2：化合物57的合成
在氮气保护下，往烧瓶中加入化合物57-1(4g，7.7mmol)，4-氰基苯频哪醇硼酸酯(2.1g，9.2mmol)和碳酸钾(2.8g，20mmol)，再加入甲苯(50mL)，乙醇(20mL)和去离子水(20mL)，醋酸钯(0.06g)和X-phos(0.12g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.9g产品，收率65％。元素分析：C42H26N4，C,85.99；H,4.45；N,9.56，HRMS(ESI,m/z):[M+H]+:587.2236。
实施例4化合物73的合成
步骤1：化合物73-1的合成
在氮气保护下，往烧瓶中加入2-氯-9-溴-菲(5g，17.1mmol)，2,4-二苯基-6-(3-苯基硼酸频哪酯)-1,3,5-三嗪(7.5g，17.1mmol)和碳酸钾(5.5g，40mmol)，再加入甲苯(50mL)，乙醇(20mL)和去离子水(20mL)，四三苯基膦钯(0.1g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到7.3g产品，收率82％。HRMS(ESI,m/z):[M+H]+:520.1583。
步骤2：化合物73的合成
在氮气保护下，往烧瓶中加入化合物73-1(6g，11.5mmol)，4-氰基苯频哪醇硼酸酯(3.2g，13.8mmol)和碳酸钾(4.1g，30mmol)，再加入甲苯(80mL)，乙醇(40mL)和去离子水(40mL)，醋酸钯(0.1g)和X-phos(0.2g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到4.6g产品，收率71％。元素分析：C42H26N4，C,85.97；H,4.49；N,9.54，HRMS(ESI,m/z):[M+H]+:587.2232。
实施例5化合物92的合成
步骤1：化合物92-1的合成
在氮气保护下，往烧瓶中加入2-氯-9-溴-菲(2.5g，8.6mmol)，2-苯基-4-(4-联苯基)-6-(3-苯基硼酸频哪酯)-1,3,5-三嗪(4.4g，8.6mmol)和碳酸钾(2.8g，20mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，四三苯基膦钯(0.05g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到4g产品，收率78％。HRMS(ESI,m/z):[M+H]+:596.1894。
步骤2：化合物92的合成
在氮气保护下，往烧瓶中加入化合物92-1(4g，6.7mmol)，3-氰基苯频哪醇硼酸酯(1.9g，8.1mmol)和碳酸钾(2.1g，15mmol)，再加入甲苯(40mL)，乙醇(20mL)和去离子水(20mL)，醋酸钯(0.05g)和X-phos(0.1g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到3g产品，收率68％。元素分析：C48H30N4，C,86.97；H,4.55；N,8.48，HRMS(ESI,m/z):[M+H]+:663.2549。
实施例6化合物103的合成
步骤1：化合物103-1的合成
在氮气保护下，往烧瓶中加入2-氯-9-溴-菲(2g，6.9mmol)，2-苯基-4-(3-二苯并呋喃基)-6-(3-苯基硼酸频哪酯)-1,3,5-三嗪(3.6g，6.9mmol)和碳酸钾(2g，15mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，四三苯基膦钯(0.05g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到3.5g产品，收率83％。HRMS(ESI,m/z):[M+H]+:611.10957。
步骤2：化合物103的合成
在氮气保护下，往烧瓶中加入化合物103-1(3.2g，5.3mmol)，4-氰基苯频哪醇硼酸酯(1.4g，6.3mmol)和碳酸钾(1.4g，10mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，醋酸钯(0.05g)和X-phos(0.1g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.7g产品，收率74％。元素分析：C48H28N4O，C,85.17；H,4.18；N,8.26；O,2.39，HRMS(ESI,m/z):[M+H]+:677.2344。
实施例7化合物116的合成
步骤1：化合物116-1的合成
在氮气保护下，往烧瓶中加入2-氯-10-溴-菲(2g，6.9mmol)，2-苯基-4-(1-二苯并呋喃基)-6-(3-苯基硼酸频哪酯)-1,3,5-三嗪(3.6g，6.9mmol)和碳酸钾(2g，15mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，四三苯基膦钯(0.05g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到3.2g产品，收率77％。HRMS(ESI,m/z):[M+H]+:610.1683。
步骤2：化合物116的合成
在氮气保护下，往烧瓶中加入化合物116-1(3g，4.9mmol)，4-氰基苯频哪醇硼酸酯(1.4g，5.9mmol)和碳酸钾(1.4g，10mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，醋酸钯(0.05g)和X-phos(0.1g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.3g产品，收率70％。元素分析：C48H28N4O，C,85.21；H,4.14；N,8.24；O,2.41，HRMS(ESI,m/z):[M+H]+:677.2345。
实施例8化合物133的合成
步骤1：化合物133-1的合成
在氮气保护下，往烧瓶中加入3-氯-10-溴-菲(2g，6.9mmol)，2-苯基-4-(2-萘基)-6-(3-苯基硼酸频哪酯)-1,3,5-三嗪(3.3g，6.9mmol)和碳酸钾(2g，15mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，四三苯基膦钯(0.05g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.7g产品，收率70％。HRMS(ESI,m/z):[M+H]+:570.1733。
步骤2：化合物133的合成
在氮气保护下，往烧瓶中加入化合物133-1(2.5g，4.4mmol)，4-氰基苯频哪醇硼酸酯(1.2g，5.3mmol)和碳酸钾(1.4g，10mmol)，再加入甲苯(20mL)，乙醇(10mL)和去离子水(10mL)，醋酸钯(0.05g)和X-phos(0.1g)，加热回流反应5h，冷却，过滤，滤饼水洗至中性，烘干，再用甲苯重结晶，过滤，干燥，得到2.1g产品，收率75％。元素分析：C46H28N4，C,86.73；H,4.45；N,8.82，HRMS(ESI,m/z):[M+H]+:637.2392。
以下通过实施例对本发明化合物的效果进行详细说明。
有机电致发光器件的制备，结构示意图见图1，具体器件结构如下：玻璃/阳极(ITO)/空穴注入层(HIL)/空穴传输层(HTL)/电子阻挡层(EBL)/发光层(主体材料BH:蓝色发光材料BD，重量比为96：4)/电子传输层(电子传输材料:8-羟基喹啉锂，重量比为50：50)/电子注入层(LiF)/阴极(Al)。
实施例9
使用实施例1的化合物14制备OLED
1、将透明导电ITO玻璃基板110(上面带有阳极120)(中国南玻集团股份有限公司)在商用清洗剂中超声处理，在去离子水中冲洗，再依次经过乙醇，丙酮和去离子水洗净，在洁净环境下烘烤至完全除去水分，用紫外光合臭氧清洗，再用氧等离子处理30秒。
2、把上述带有阳极的玻璃基片至于真空腔内，抽真空，在ITO上面蒸镀HIL(2nm)作为空穴注入层130，蒸镀速率为0.1nm/s。
3、在空穴注入层上面蒸镀化合物HT，形成100nm厚的空穴传输层140，蒸镀速率为0.1nm/s，
4、在空穴传输层上面蒸镀EB，形成10nm厚的电子阻挡层150。蒸镀速率为0.1nm/s。
5、在空穴阻挡层上蒸镀30nm厚的发光层160，其中，BH为主体发光材料，而以4％重量比的BD作为掺杂客体材料，蒸镀速率为0.1nm/s。
6、在发光层上蒸镀30nm厚的化合物14和LiQ(化合物14：LiQ，重量比为50：50)作为电子传输层170。蒸镀速率为0.1nm/s，
7、蒸镀1nm LiF为电子注入层180和Al作为器件阴极190。
实施例10
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物48和LiQ作为电子传输层170。
实施例11
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物57和LiQ作为电子传输层170。
实施例12
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物73和LiQ作为电子传输层170。
实施例13
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物92和LiQ作为电子传输层170。
实施例14
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物103和LiQ作为作为电子传输层170。
实施例15
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物116和LiQ作为电子传输层170。
实施例16
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物133和LiQ作为电子传输层170。
对比例1
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物ET1和LiQ作为电子传输层170。
对比例2
与实施例9的区别仅在于，步骤5中在发光层上蒸镀30nm厚的化合物ET2和LiQ作为电子传输层170。
将本发明实施例9-14和对比例1-2所制备的器件用Photo Research PR650光谱仪测得在50mA/cm2的电流密度下的工作电压，亮度，效率。具体如表1所示，图5为实施例9-13的电压与亮度关系图；图6为实施例9-13的电流密度与电流效率关系图。
表1
由表1、图5和图6的实验数据可以看出，具有化学式I表示的本发明化合物可以作为电子传输材料应用于有机电致发光器件。
本发明含氮原子杂环和苯甲腈的有机电子材料制备的有机电致发光器件在相同的电流密度下，工作电压比现有技术对比例1-2低，亮度高，电流效率、功率效率和外量子效率都得到提升。这是由于在相同的电流密度下，由于本发明引入了大平面结构菲基团和强电子传输能力苯甲腈基团，使得化合物具有更好的电子传输能力，制备的器件具有更低的工作电压，消耗较小的功耗，提高器件的效率和寿命。对比ET1在菲的9，10位上都有苯环，而本发明的9，10位上面一个位置连接苯环，一个位置连接氢原子，由于氢原子具有更小的原子体积，从而减小苯基与菲之间的夹角，增加共轭，有利于提升化合物的电子迁移率；对比ET2菲连接的芳基，而本发明连接的是苯甲腈，更强的电负性，也有利于提升化合物的电子迁移率，因此，本发明的化合物制备的器件比ET1和ET2制备的比较例1和2的效率提升，电压降低。同时，在菲的不同位置引入氮原子杂环和苯甲腈为不对称的基团，既可以降低不同基团的相互影响，又可以提高材料的热稳定性，有利于制备无定形薄膜，提高器件效率和延长器件寿命。
器件中所述结构式如下：
上述有机材料都是现有的已知材料，由市场采购获得。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
Claims (3)
1.一种含有氮原子杂环和苯甲腈的有机电子传输材料，其特征在于，其结构通式如式I所示，
Ar1和Ar2为苯基，联苯基，萘基，9,9-二甲基芴基，二苯并呋喃基，二苯并噻吩基中的一种；
Z1、Z2和Z3中至少有一个为N，其它为CH；
R为氢，甲基，氘中的一种；
R1-R8中有一个为苯甲腈基，其他的为氢。
2.一种权利要求1所述的含有氮原子杂环和苯甲腈的有机电子传输材料的应用，其特征在于，所述的有机电子材料可被用于生产有机电致发光器件、有机太阳能电池、有机薄膜晶体管、有机光检测器、有机场效应晶体管、有机集成电路和有机光感受器。
3.根据权利要求2所述的含有氮原子杂环和苯甲腈的有机电子传输材料的应用，其特征在于，有机电致发光器件包括阳极、阴极和有机层，有机层包含发光层、空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层以上，有机层中至少有一层含有上述的有机电子材料。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110106379.4A CN112898199B (zh) | 2021-01-26 | 2021-01-26 | 一种含有氮原子杂环和苯甲腈的有机电子传输材料及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110106379.4A CN112898199B (zh) | 2021-01-26 | 2021-01-26 | 一种含有氮原子杂环和苯甲腈的有机电子传输材料及其应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112898199A CN112898199A (zh) | 2021-06-04 |
| CN112898199B true CN112898199B (zh) | 2022-11-11 |
Family
ID=76120432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110106379.4A Active CN112898199B (zh) | 2021-01-26 | 2021-01-26 | 一种含有氮原子杂环和苯甲腈的有机电子传输材料及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112898199B (zh) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101833171B1 (ko) * | 2016-05-30 | 2018-02-27 | 주식회사 엘지화학 | 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자 |
| KR101904659B1 (ko) * | 2016-06-01 | 2018-10-04 | 주식회사 엘지화학 | 신규한 화합물 및 이를 포함하는 유기 발광 소자 |
| CN111170993B (zh) * | 2020-01-08 | 2020-12-22 | 上海传勤新材料有限公司 | 一种含有氮原子杂环的有机电子材料及其制备方法和应用 |
| CN111187228B (zh) * | 2020-02-04 | 2023-08-01 | 上海传勤新材料有限公司 | 一种基于菲和苯甲腈的有机电子材料及其应用 |
| CN111704580A (zh) * | 2020-06-07 | 2020-09-25 | 上海传勤新材料有限公司 | 一种含苯并咪唑的化合物及其在有机电致发光器件中的应用 |
-
2021
- 2021-01-26 CN CN202110106379.4A patent/CN112898199B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112898199A (zh) | 2021-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2719743B1 (en) | Novel compounds and organic electronic device using same | |
| EP2215183B1 (en) | New compound and organic light emitting device using the same | |
| KR101244599B1 (ko) | 바이폴라 트리페닐렌계 화합물 및 이를 포함하는 유기 전계 발광 소자 | |
| EP2376594B1 (en) | Compound for organic photoelectric device and organic photoelectric device including the same | |
| JP5638612B2 (ja) | 新規な複素環誘導体およびこれを用いた有機発光素子 | |
| JP5432147B2 (ja) | 有機金属錯体誘導体およびこれを用いた有機発光素子 | |
| JP5154569B2 (ja) | 新規なフルオレン誘導体およびこれを用いた有機電子素子 | |
| KR102250389B1 (ko) | 유기발광소자 | |
| EP2862862B1 (en) | Organic light emitting device comprising nitrogen-containing heterocyclic compound | |
| CN109608453B (zh) | 一种以4，7-二氮杂菲为受体的化合物及其应用 | |
| KR101597865B1 (ko) | 신규한 화합물 및 이를 이용한 유기 전자 소자 | |
| JP2011506564A (ja) | ナフチル置換されたアントラセン誘導体および有機発光ダイオードにおけるその使用 | |
| JP2017522732A (ja) | 電子輸送物質およびそれを含む有機エレクトロルミネセント素子 | |
| CN106892903B (zh) | 基于酚嗪和咔唑的有机电致发光化合物及其发光器件 | |
| KR20110057008A (ko) | 신규한 디아민 유도체, 이의 제조방법 및 이를 이용한 유기 전자 소자 | |
| CN113372289A (zh) | 一种含有菲并唑类化合物的有机电子材料及其制备方法和应用 | |
| KR20150082156A (ko) | 신규한 화합물 및 이를 포함하는 유기 발광 소자 | |
| CN114437032B (zh) | 一种含有四联苯的化合物及其应用 | |
| KR20200068568A (ko) | 신규한 화합물 및 이를 포함하는 유기발광 소자 | |
| WO2022131123A1 (ja) | 有機電界発光素子及びその製造方法 | |
| CN112898199B (zh) | 一种含有氮原子杂环和苯甲腈的有机电子传输材料及其应用 | |
| CN111018863B (zh) | 一种以吡咯[1，2-a]并喹喔啉为受体的化合物及其应用 | |
| CN113336771A (zh) | 一种稠环咔唑衍生物及其有机电致发光器件 | |
| CN112552251A (zh) | 一种含有氘原子的有机电子材料及其应用 | |
| CN111233832A (zh) | 一种含有芴和三嗪的有机电子材料及其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |