CN114644617A - Cyanopyridine compound and electroluminescent device comprising the same - Google Patents
Cyanopyridine compound and electroluminescent device comprising the same Download PDFInfo
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- CN114644617A CN114644617A CN202011510063.3A CN202011510063A CN114644617A CN 114644617 A CN114644617 A CN 114644617A CN 202011510063 A CN202011510063 A CN 202011510063A CN 114644617 A CN114644617 A CN 114644617A
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- compound
- cyanopyridine
- light emitting
- synthesis
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- -1 Cyanopyridine compound Chemical class 0.000 title claims abstract description 60
- 239000000126 substance Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims description 117
- 239000000463 material Substances 0.000 claims description 46
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 230000000903 blocking effect Effects 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 230000005525 hole transport Effects 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 description 73
- 238000003786 synthesis reaction Methods 0.000 description 73
- 239000010410 layer Substances 0.000 description 68
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 58
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 36
- 230000003111 delayed effect Effects 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000002019 doping agent Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000004770 highest occupied molecular orbital Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 14
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000005281 excited state Effects 0.000 description 12
- 238000001296 phosphorescence spectrum Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 11
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 7
- KXMHPELKLKNUCC-UHFFFAOYSA-N 9-(3-carbazol-9-ylphenyl)carbazole-3-carbonitrile Chemical compound N#CC1=CC2=C(C=C1)N(C1=C2C=CC=C1)C1=CC(=CC=C1)N1C2=C(C=CC=C2)C2=C1C=CC=C2 KXMHPELKLKNUCC-UHFFFAOYSA-N 0.000 description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 7
- 239000005695 Ammonium acetate Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 235000019257 ammonium acetate Nutrition 0.000 description 7
- 229940043376 ammonium acetate Drugs 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000001443 photoexcitation Effects 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000859 sublimation Methods 0.000 description 7
- 230000008022 sublimation Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ZJRCIQAMTAINCB-UHFFFAOYSA-N benzoylacetonitrile Chemical compound N#CCC(=O)C1=CC=CC=C1 ZJRCIQAMTAINCB-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 238000004776 molecular orbital Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- UHPIOPMELXIDLL-UHFFFAOYSA-N pyridine-3,5-dicarbonitrile Chemical compound N#CC1=CN=CC(C#N)=C1 UHPIOPMELXIDLL-UHFFFAOYSA-N 0.000 description 6
- 125000004076 pyridyl group Chemical group 0.000 description 6
- 210000002966 serum Anatomy 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000007725 thermal activation Methods 0.000 description 5
- MMNNWKCYXNXWBG-UHFFFAOYSA-N 2,4,6-tris(3-phenylphenyl)-1,3,5-triazine Chemical group C1=CC=CC=C1C1=CC=CC(C=2N=C(N=C(N=2)C=2C=C(C=CC=2)C=2C=CC=CC=2)C=2C=C(C=CC=2)C=2C=CC=CC=2)=C1 MMNNWKCYXNXWBG-UHFFFAOYSA-N 0.000 description 4
- MZYDBGLUVPLRKR-UHFFFAOYSA-N 9-(3-carbazol-9-ylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 MZYDBGLUVPLRKR-UHFFFAOYSA-N 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 230000005283 ground state Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 4
- 238000004227 thermal cracking Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- FXKMXDQBHDTQII-UHFFFAOYSA-N 9-phenyl-3,6-bis(9-phenylcarbazol-3-yl)carbazole Chemical compound C1=CC=CC=C1N1C2=CC=C(C=3C=C4C5=CC(=CC=C5N(C=5C=CC=CC=5)C4=CC=3)C=3C=C4C5=CC=CC=C5N(C=5C=CC=CC=5)C4=CC=3)C=C2C2=CC=CC=C21 FXKMXDQBHDTQII-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- YAELXYZSNJSOCR-UHFFFAOYSA-N 2-pyridin-2-yl-5-[7-(6-pyridin-2-ylpyridin-3-yl)triphenylen-2-yl]pyridine Chemical group N1=CC=CC=C1C1=CC=C(C=2C=C3C4=CC=CC=C4C4=CC(=CC=C4C3=CC=2)C=2C=NC(=CC=2)C=2N=CC=CC=2)C=N1 YAELXYZSNJSOCR-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- NSXJEEMTGWMJPY-UHFFFAOYSA-N 9-[3-(3-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(C=2C=CC=C(C=2)N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 NSXJEEMTGWMJPY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 description 2
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
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- 150000004696 coordination complex Chemical class 0.000 description 2
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
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- RFDGVZHLJCKEPT-UHFFFAOYSA-N tris(2,4,6-trimethyl-3-pyridin-3-ylphenyl)borane Chemical compound CC1=C(B(C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C(C)=CC(C)=C1C1=CC=CN=C1 RFDGVZHLJCKEPT-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LUBKKVGXMXTXOZ-QGZVFWFLSA-N (+)-geodin Chemical compound COC(=O)C1=CC(=O)C=C(OC)[C@@]11C(=O)C(C(O)=C(Cl)C(C)=C2Cl)=C2O1 LUBKKVGXMXTXOZ-QGZVFWFLSA-N 0.000 description 1
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical compound N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- HJUCYZCLVXUJJD-UHFFFAOYSA-N 10-(4-bromo-3,5-dimethylphenyl)spiro[acridine-9,9'-fluorene] Chemical compound CC1=CC(N2C3=CC=CC=C3C3(C4=CC=CC=C4C4=C3C=CC=C4)C3=C2C=CC=C3)=CC(C)=C1Br HJUCYZCLVXUJJD-UHFFFAOYSA-N 0.000 description 1
- WQNLIQLHZXTVJQ-UHFFFAOYSA-N 11-(4-bromo-3,5-dimethylphenyl)benzo[b][1]benzazepine Chemical compound CC1=CC(N2C(C=CC=C3)=C3C=CC3=C2C=CC=C3)=CC(C)=C1Br WQNLIQLHZXTVJQ-UHFFFAOYSA-N 0.000 description 1
- WCFXSCGDJQUGOT-UHFFFAOYSA-N 2,6-dimethyl-4-(N-phenylanilino)benzaldehyde Chemical compound CC1=C(C=O)C(C)=CC(N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 WCFXSCGDJQUGOT-UHFFFAOYSA-N 0.000 description 1
- DFRKLHCRHAQVEX-UHFFFAOYSA-N 2,6-diphenyl-4-[4-(N-phenylanilino)phenyl]pyridine-3,5-dicarbonitrile Chemical compound C1(=CC=CC=C1)N(C1=CC=C(C=C1)C1=C(C(=NC(=C1C#N)C1=CC=CC=C1)C1=CC=CC=C1)C#N)C1=CC=CC=C1 DFRKLHCRHAQVEX-UHFFFAOYSA-N 0.000 description 1
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- FFPUWZLVEGMKAR-UHFFFAOYSA-N 9-(4-bromo-3,5-dimethylphenyl)-3,6-ditert-butylcarbazole Chemical compound BrC1=C(C=C(C=C1C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(C)(C)C)C(C)(C)C)C FFPUWZLVEGMKAR-UHFFFAOYSA-N 0.000 description 1
- NGBCWSNMYKYNQB-UHFFFAOYSA-N 9-(4-bromo-3,5-dimethylphenyl)carbazole Chemical compound CC1=C(Br)C(C)=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=C1 NGBCWSNMYKYNQB-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 238000005284 basis set Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BKMIWBZIQAAZBD-UHFFFAOYSA-N diindenoperylene Chemical compound C12=C3C4=CC=C2C2=CC=CC=C2C1=CC=C3C1=CC=C2C3=CC=CC=C3C3=CC=C4C1=C32 BKMIWBZIQAAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QPJFIVIVOOQUKD-UHFFFAOYSA-N dipyrazino[2,3-f:2,3-h]quinoxaline Chemical group C1=CN=C2C3=NC=CN=C3C3=NC=CN=C3C2=N1 QPJFIVIVOOQUKD-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005223 heteroarylcarbonyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000004735 phosphorescence spectroscopy Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000004402 ultra-violet photoelectron spectroscopy Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 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
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- 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
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- 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
- C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
A cyanopyridine compound represented by chemical formula 1 and an electroluminescent device comprising the same. In chemical formula 1, R1To R3、Ar1And Ar2As described in the detailed description. [ chemical formula 1]
Description
Technical Field
The present invention relates to a compound, and more particularly, to a cyanopyridine compound and an electroluminescent device comprising the same.
Background
Conventional fluorescent materials can be used as emitters in Organic Light Emitting Diode (OLED) assemblies. Due to the spin selection rule (spin selection rule), the ratio of excitons used is low, which results in insufficient light emitting efficiency of the light emitting device. In the prior art, noble metals are introduced into the phosphor materials to increase Spin-Orbital Coupling (SOC) effect, thereby improving the light emitting efficiency of the light emitting device. However, since the precious metals (e.g. iridium and platinum) are expensive, the manufacturing cost of the light emitting device is also increased, which is not suitable for commercial application.
The development of Thermally Activated Delayed Fluorescence (TADF) materials has been a popular field of research in recent years, wherein TADF materials have the advantages of both high luminous efficiency and low cost. The key to making the luminescent molecule possess the property of thermally activated delayed fluorescence is to narrow down the lowest singlet excited state (S)1) And the lowest triplet excited state (T)1) Energy difference (Δ E) therebetweenST). When Δ ESTSmall enough, the endothermic Reverse Intersystem Crossing (RISC) can occur via thermal activation stimulation of the environment and capture 25% of singlet excitons and 75% of triplet excitons simultaneously during electrical excitation, thereby achieving 100% internal quantum efficiency.
However, too small Δ ESTThis results in a decrease in the ability to transition between the excited state and the ground state, and an increase in the occurrence of non-radiative paths, which in turn decreases the luminescence Quantum efficiency (PLQY). Therefore, the structural design of the light-emitting molecules determines the light-emitting characteristics of the material.
Furthermore, the Delayed Fluorescence lifetime (Delayed Fluorescence lifetime) of the typical TADF material is long, about tens to hundreds of microseconds (microsecond), while the excitons at high energy are easily quenched, which limits the efficiency performance and the operation stability of the light emitting device at high brightness, thereby reducing the reliability and lifetime performance of the typical TADF material applied to the electroluminescent device.
Disclosure of Invention
The present invention provides a cyanopyridine compound which can realize an electroluminescent module having high luminous efficiency.
The present invention provides a cyanopyridine compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the reaction mixture is,
Ar1and Ar2May be the same or different and are each independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl;
R1and R2May be the same or different and are each independently substituted or unsubstituted alkyl; and
R3is a nitrogen-containing group.
In one embodiment of the present invention, R3Any one selected from the following structures:
in one embodiment of the present invention, Ar1And Ar2Each independently is any one selected from the following structures:
in one embodiment of the present invention, R1And R2Each independently being methyl, ethyl or propyl.
In an embodiment of the present invention, the cyanopyridine compound is selected from the following structural formulas:
the present invention provides an electroluminescence device, including: a cathode, an anode, and a light-emitting layer. The light-emitting layer is arranged between the cathode and the anode, and the light-emitting layer comprises the cyanopyridine compound.
In an embodiment of the invention, the light emitting layer includes a host light emitting material and a guest light emitting material.
In an embodiment of the invention, the host luminescent material includes the cyanopyridine compound.
In an embodiment of the invention, the guest light emitting material includes the cyanopyridine compound.
In an embodiment of the invention, the electroluminescent device further includes at least one auxiliary layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an exciton blocking layer, an electron injection layer, an electron transport layer and an electron blocking layer.
Based on the above, the cyanopyridine compound of the present example has characteristics satisfying the requirement of multiple optical rotation, high luminescence quantum efficiency, excellent thermal stability and thermally activated delayed fluorescence. The cyano pyridine-containing compound of the invention increases the electron accepting ability of the pyridine group by introducing cyano groups at the 3-and 5-positions of the pyridine group. In addition, the cyanopyridine-containing compounds of the present invention have 3, 5-dicyanopyridine as an electron-withdrawing group, thereby increasing the charge transfer properties of the whole molecule and narrowing the electron cloud overlap of HOMO and LUMO to decrease Δ ESTThereby obtaining the thermal activation delayed fluorescence characteristic and further improving the luminous efficiency of the electroluminescent device.
In addition, in the present embodiment, since the cyanopyridine-containing compound introduces the nitrogen-containing group as an electron donor at the para position of the phenyl group as the linking group, the emission color and the emission Quantum efficiency of the molecule can be controlled (PLQY). In addition, in this example, since the cyanopyridine-containing compound has an alkyl group introduced at the ortho-position of the phenyl group as the linking group, the dihedral angle (dihedral angle) between the phenyl group and the 3, 5-dicyanopyridine is increased by the steric hindrance effect between the alkyl group and the cyano group, and the overlap of the electron clouds of the HOMO and LUMO is reduced. In addition, the light-emitting layer of the electroluminescent device of the present embodiment includes the cyanopyridine compound, and thus has high external quantum efficiency and long lifetime of the light-emitting element.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a cross-sectional view of an electroluminescent device according to an embodiment of the present invention;
FIG. 2 is a cross-sectional view of an electroluminescent device according to another embodiment of the present invention;
FIG. 3 is an electron cloud distribution plot of the Molecular Orbital (MO) domains of TPAPPC, TPAsPPC and TPAmPPC;
fig. 4 is an ultraviolet-visible absorption (UV-vis absorbance) spectrum of compounds of synthesis examples 8 to 13 and synthesis comparative example 1;
FIG. 5 is a photoexcitation emission spectrum of the compounds of Synthesis examples 8 to 13 and Synthesis comparative example 1;
FIG. 6 is a room temperature fluorescence spectrum and a low temperature phosphorescence spectrum of CZmPPC according to an embodiment of the present invention;
FIG. 7 shows a room temperature fluorescence spectrum and a low temperature phosphorescence spectrum of TPAmPPC according to an embodiment of the present invention;
FIG. 8 is a room temperature fluorescence spectrum and a low temperature phosphorescence spectrum of tCzmPPC according to an embodiment of the present invention;
FIG. 9 shows a room temperature fluorescence spectrum and a low temperature phosphorescence spectrum of TPAPPC according to an embodiment of the present invention;
fig. 10 is photoexcitation emission spectra of the organic light emitting diodes of experimental examples 1 to 6;
fig. 11 is a luminance-external quantum efficiency curve of the organic light emitting diodes of experimental example 5, comparative example 1, and comparative example 2;
fig. 12 is a luminance-external quantum efficiency curve of the organic light emitting diodes of experimental example 2 and comparative example 3;
fig. 13 is a luminance-external quantum efficiency curve of the organic light emitting diode of experimental example 5 at different temperatures;
fig. 14 shows the results of the lifetime test of the light-emitting devices of experimental example 10, experimental example 11, and comparative example 4.
[ description of symbols ]
10. 20: an electroluminescence device;
102: an anode;
103: a hole transport layer;
104: a cathode;
105: an electron transport layer;
106: and a light emitting layer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments that can be derived by a person skilled in the art from the embodiments and the drawings based on the embodiments of the present invention are within the scope of the claims of the present invention.
In the description of the present invention, it should be noted that the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art to which the invention pertains, and the present invention will only be defined by the scope of the appended claims. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity. It will be understood that when an element such as a layer is referred to as being "formed on" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly formed on" or "directly disposed on" another element, there are no intervening elements present.
In the context of the present specification,
meaning a moiety attached to another substituent.
In the present specification, the term "substituted" means substituted by the following groups, if not otherwise defined: halogen, aryl, hydroxy, alkenyl, C1-C20Alkyl, alkynyl, cyano, trifluoromethyl, alkylamino, amino, C1-C20Alkoxy, heteroaryl, aryl with halogen substituent, aralkyl with halogen substituent, aryl with haloalkyl substituent, aralkyl with haloalkyl substituent, C with aryl substituent1-C20Alkyl, cycloalkyl, having C1-C20An amino group having an alkyl substituent, an amino group having a haloalkyl substituent, an amino group having an aryl substituent, an amino group having a heteroaryl substituent, a phosphonooxy group having an aryl substituent, a phosphonooxy group having C1-C20Alkyl-substituted phosphonoxy, phosphonooxy with haloalkyl substituent, phosphonooxy with halogen substituent, phosphonooxy with heteroaryl substituent, nitro, carbonyl, arylcarbonyl, heteroarylcarbonyl or C with halogen substituent1-C20An alkyl group.
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are illustrative, and the present invention is not limited thereto.
A cyanopyridine compound according to an embodiment of the present invention is represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the first and second,
Ar1and Ar2May be the same or different and are each independently a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl;
R1and R2May be the same or different and are each independently substituted or unsubstituted alkyl; and
R3is a nitrogen-containing group.
In one embodiment of the present invention, R3Any one selected from the following structures:
in one embodiment of the present invention, Ar1And Ar2Each independently is any one selected from the following structures:
in one embodiment of the present invention, R1And R2Each independently methyl, ethyl or propyl.
In one embodiment of the present invention, the cyanopyridine-containing compound is selected from any one of the following structural formulas:
in this example, the cyanopyridine-containing compound of the present invention has a core structure of 3, 5-dicyanopyridine, and this core structure can serve as an electron acceptor (i.e., electron-withdrawing group). Further, the 4-position of the pyridine group of the cyanopyridine compound of the present invention is linked with a phenyl group (as a linking group), and a nitrogen-containing group (R) as an electron donor (i.e., electron donating group) is introduced at the para-position of the phenyl group3). Further, the cyanopyridine-containing compound of the present invention has alkyl groups (R) introduced at the ortho-positions of the phenyl groups as the linking groups, respectively1And R2) And in the pyridine group (as core structure)) The 2 nd and 6 th positions of the compound are respectively introduced with aryl or heteroaryl with resonance property.
Because the pyridine group has insufficient electron withdrawing capability, the cyanopyridine compound of the present invention has cyano groups introduced into the positions 3 and 5 of the pyridine group to increase the electron accepting capability of the pyridine group. In addition, the cyanopyridine compound of the present invention has 3, 5-dicyanopyridine as an electron withdrawing group to increase the charge transfer property of the whole molecule and to reduce the overlap of electron clouds of HOMO and LUMO to decrease Δ ESTTherefore, the thermal activation delayed fluorescence characteristic is obtained, and the luminous efficiency of the OLED component can be improved.
Further, in this example, since the cyanopyridine-containing compound was introduced with the nitrogen-containing group (R) as the electron donor at the para-position of the phenyl group as the linking group3) Thereby, the light emission color and the light emission Quantum efficiency of the molecule (PLQY) can be controlled. In addition, in this example, since the cyanopyridine compound was introduced with alkyl groups (R) respectively at the ortho-positions to the phenyl groups as the linking groups1And R2) The dihedral angle (dihedral angle) between the phenyl group and the 3, 5-dicyanopyridine is increased by the steric hindrance effect between the alkyl group and the cyano group, thereby achieving the purpose of reducing the electron cloud overlap of HOMO and LUMO.
Hereinafter, an organic light emitting diode according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of an electroluminescent device according to an embodiment of the invention.
Referring to fig. 1, the electroluminescent device 10 of the present embodiment includes an anode 102, a cathode 104 and a light-emitting layer 106. In one embodiment, the electroluminescent device 10 is an Organic Light Emitting Diode (OLED). The light emitting layer 106 is disposed between the anode 102 and the cathode 104. The anode 102 may be made of a conductor having a high work function to assist hole injection into the light emitting layer 106. The material of the anode 102 is, for example, a metal oxide, a conductive polymer, or a combination thereof. Specifically, the metal is, for example, nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; the metal oxide is, for example, zinc oxide, indium tin oxide(ITO) or Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO with Al or SnO2In combination with Sb; the conductive polymer is, for example, poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene (poly (3,4- (ethylene-1,2-dioxy) thiophene, PEDT), polypyrrole (polypyrole), or polyaniline (polyailine), but the present invention is not limited thereto.
The cathode 104 may be made of a conductor having a low work function to assist electron injection into the light emitting layer 106. The material of the cathode 104 is, for example, a metal or a material of a multilayer structure. Specifically, the metal is, for example, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium (gadolinium), aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; the material of the multilayer structure is, for example, LiF/Al, LiO2Al, LiF/Ca, LiF/Al or BaF2The present invention is not limited thereto.
In this embodiment, the light-emitting layer 106 includes the cyanopyridine compound of the above-described embodiment. Specifically, the light-emitting layer 106 includes a mixture of at least one of the cyanopyridine-containing compounds of the above-described embodiments, at least two of the cyanopyridine-containing compounds of the above-described embodiments, or the cyanopyridine-containing compounds of the above-described embodiments with other compounds.
The light-emitting layer 106 typically includes a host light-emitting material and a guest light-emitting material. In one embodiment, the cyanopyridine-containing compound of the above embodiments can be used as a host light-emitting material to be mixed with a guest light-emitting material. In one embodiment, the light-emitting layer 106 may include a cyanopyridine-containing compound and other host light-emitting materials. In one embodiment, the cyanopyridine-containing compound of the above embodiments can be used as a guest light-emitting material and mixed with a host light-emitting material.
The host light-emitting material other than the cyanopyridine compound of the above embodiment is, for example, a condensed aromatic ring derivative (condensed aromatic ring derivative), a heterocyclic ring-containing compound (heterocyclic-containing compound), or the like. The fused aromatic ring derivative is, for example, an anthracene (anthrene) compound, a pyrene (pyrene) compound, a naphthalene (naphthalene) compound, a pentacene (pentacene) compound, a phenanthrene (phenanthrene) compound, a fluoranthene (fluoranthene) compound, or the like. The heterocycle-containing compound is, for example, a carbazole compound, a dibenzofuran (dibenzofuran) compound, a ladder-type furan (ladder-type furan) compound, a pyrimidine (pyrimidine) compound, or the like.
The guest light-emitting material other than the cyanopyridine-containing compound of the above-described embodiment is, for example, an arylamine compound, a styrylamine compound, a boron complex (boron complex), a fluoranthene compound, a metal complex, or the like. Specifically, the arylamine compound is, for example, a fused aromatic ring compound substituted with an arylamine group, and examples thereof include pyrene, anthracene, chrysene, diindenopyrene (periflanthene), and the like having an arylamine group; specific examples of the styrene amine compound include styrene amine (styryl amine), styrene diamine (styryl diamine), styrene triamine (styryl triamine), and styrene tetramine (styryl tetramine). Examples of the metal complex include iridium complex (iridium complex) and platinum complex (platinum complex), but are not limited thereto.
In one embodiment, the organic light emitting diode 10 further comprises at least one auxiliary layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an exciton blocking layer, an electron injection layer, an electron transport layer, and an electron blocking layer.
FIG. 2 is a cross-sectional view of an electroluminescent device according to another embodiment of the present invention. In fig. 2, the same components as those in fig. 1 will be denoted by the same reference numerals, and the description of the same technical contents will be omitted. The electroluminescent device 20 includes an anode 102, a hole transport layer 103, a light-emitting layer 106, an electron transport layer 105, and a cathode 104. In the present embodiment, the light-emitting layer 106 includes the cyanopyridine-containing compound of the above-described embodiment.
Hereinafter, the above embodiments are described in more detail with reference to examples. However, these examples are not to be construed in any way as limiting the scope of the invention.
[ theoretical calculation of Density functional ]
In this example, the compounds CzmPPC, tCzmPPC, SAcmPPC, TPAmPPC, tTPAmPPC, DP were obtained by calculation using Density Functional Theory (DFT)Optimum structure (geometrical optimization) of CzmPPC, TPAepPC, TPAiPPC, TPAmPPCcn and TPAmPPCph, and singlet excited state energy (E)S) Triplet excited state energy (E)T)、ΔESTAnd dihedral angles, and further predict the possibility of the cyanopyridine-containing compounds of the present invention as Thermally Activated Delayed Fluorescence (TADF) materials.
In this example, using Gaussian09 as the computing software, B3LYP calculations were performed and the transition energy from the ground state to the excited state and the electron cloud distribution were calculated with Time-dependent density functional theory (TD-DFT) with 6-31G as the basis function (basis set).
The results of theoretical calculations are shown in table 1 below, where the dihedral angle (dihedral angle) is defined as the angle between the 3, 5-dicyanopyridine and the phenyl group in position 4.
[ Table 1]
From the results shown in Table 1, it is understood that the singlet excited state energy (E) of the cyanopyridine-containing compound of the present invention is theoretically calculatedS) With energy of triplet excited state (E)T) Difference Δ E betweenST0.0001-0.078 eV, and a dihedral angle of 73.7-89.1 deg. The above-mentioned low Δ E can be achievedSTAnd the reason for the high dihedral angle is that the steric hindrance between the alkyl group at the ortho position on the phenyl group of the cyanopyridine-containing compound and the cyano group at the 3-and 5-positions of the pyridyl group shifts the two planes to be nearly orthogonal, making the orbital overlap between the HOMO and LUMO small, thereby reducing Δ ESTThus, it is presumed that the cyanopyridine compounds of the present invention are thermally activatedDelayed fluorescence properties.
In this example, compounds TPAPPC, TPAsPPC were used as comparative examples. In the structure of compound TPAPPC, in the ortho position (R) of the benzene ring to which the pyridine-3, 5-dicyano group is attached1And R2) Has no substituent, i.e. R1And R2Are both hydrogen. And in the structure of the compound TPAsPPC, R1Is hydrogen, and R2Is methyl.
Calculating by density functional theory to obtain electron cloud distribution and Delta E of Molecular Orbital (MO) of compounds TPAPPC, TPAsPPC and TPAmPPCSTAnd dihedral angles. The results of the theoretical calculations are shown in table 2 below.
[ Table 2]
| Compound (I) | ΔEST(eV) | Two-sided angle (°) |
| TPAPPC | 0.224 | 50.4 |
| TPAsPPC | 0.025 | 68.2 |
| TPAmPPC | 0.015 | 73.8 |
FIG. 3 is an electron cloud distribution diagram of the Molecular Orbital (MO) domains of TPAPPC, TPAsPPC and TPAmPPC. As is clear from the results of table 2 and fig. 3, the electron cloud of the HOMO of the compound TPAmPPC is concentrated on the electron acceptor (i.e., electron-withdrawing group), and the electron cloud of the LUMO of the compound TPAmPPC is concentrated on the electron donor (i.e., electron-withdrawing group). In addition, because the alkyl group at the ortho position on the phenyl group of the compound TPAmPPC is close to the pyridyl group, the alkyl group on the phenyl group and the cyano group on the pyridyl group create a steric barrier, which allows good separation of HOMO and LUMO (i.e., the overlap of the orbital regions between HOMO and LUMO is small), thereby reducing Δ EST(only 0.015).
The trans-compound TPAPPC and TPAsPPC have a dihedral angle of only 50.4-68.2 DEG because of lack of sufficient steric hindrance at the ortho-position of the linking group (i.e., phenyl group) of the compounds TPAPPC and TPAsPPC, and the electron cloud of HOMO extends to the pyridine group, resulting in large overlap of the rail regions between HOMO and LUMO, and thus Δ ESTAnd (4) increasing.
Synthesis of organic compounds
[ intermediate Synthesis ]
Synthesis example 1: synthesis of intermediate I-1(4- (9H-carbazol-9-yl) -2,6-dimethylbenzaldehyde)
[ reaction scheme 1]
The compound 9- (4-bromo-3, 5-dimethylphenyl) -9H-carbazole (1g,2.9mmol) was added to a two-necked flask, stoppered with serum, dried Tetrahydrofuran (THF) (19mL,0.15M) was added via the side port, and the system was cooled to-78 ℃ with an acetone bath. N-butyllithium (n-butylllithium, n-BuLi) (1.73mL,4.3mmol) was slowly added to the flask in a plastic syringe under nitrogen to form an orange solution, and the acetone bath was maintained for 1 hour. Then, dry Dimethylformamide (DMF) (0.64g,8.7mmol) was added by syringe under nitrogen atmosphere, and the acetone bath was maintained for 1 hour, and the reaction was carried out overnight. After the reaction was complete, water was added and excess base was neutralized with aqueous hydrochloric acid. Extracted 3 times with ethyl acetate and concentrated by rotation. Then, the product was purified by column chromatography (eluent was ethyl acetate/n-hexane 1/19, v/v) to obtain intermediate I-1(0.69g, yield 80.0%) as a white solid.
1H NMR(500MHz,CDCl3,δ):10.67(s,1H),8.12(d,J＝8.0Hz,2H),7.48(d,J＝8.5Hz,2H),7.42(t,J＝8.0Hz,2H),7.34(s,2H),7.30(t,J＝7.5Hz,2H),2.72(s,6H).13C NMR(125MHz,CDCl3,δ):192.41,143.51,141.58,140.11,130.91,127.17,126.13,123.79,120.52,120.43,109.92,20.80.
Synthesis example 2: synthesis of intermediate I-2(4- (3,6-di-tert-butyl-9H-carbazol-9-yl) -2,6-dimethylbenzaldehyde)
[ reaction scheme 2]
The compound 9- (4-bromo-3, 5-dimethylphenyl) -3, 6-di-tert-butyl-9H-carbazole (1g,2.2mmol) was added in a two-necked flask, stoppered with serum, dried Tetrahydrofuran (THF) (14mL,0.15M) was added via the side port, and the system was cooled to-78 ℃ with an acetone bath. N-butyllithium (1.31mL,3.2mmol) was added slowly with a plastic needle under nitrogen to form an orange solution, and the acetone bath was maintained for 1 hour. Then, dry Dimethylformamide (DMF) (0.47g,6.5mmol) was added by syringe under nitrogen, and the acetone bath was maintained for 1 hour, and the reaction was carried out overnight. After the reaction was completed, water was added and the excess alkali was neutralized with an aqueous hydrochloric acid solution. Extracted 3 times with ethyl acetate and concentrated by rotation. Then, the product was purified by column chromatography (using ethyl acetate/n-hexane 1/19, v/v) to obtain intermediate I-2(0.6g, yield 67.4%) as a white solid.
1H NMR(500MHz,CDCl3,δ):10.66(s,1H),8.12(s,2H),7.45(q,J＝8.5Hz,4H),7.33(s,2H),2.71(s,6H),1.45(s,18H).13C NMR(125MHz,CDCl3,δ):192.34,143.56,143.47,142.13,138.38,130.39,126.58,123.87,123.78,116.37,109.44,34.75,31.95,20.84.
Synthesis example 3: synthesis of intermediate I-3(4- (5H-dibenzo [ b, f ] azepin-5-yl) -2,6-dimethylbenzaldehyde) (4- (5H-dibenz [ b, f ] azepin-5-yl) -2,6-dimethylbenzaldehyde)
[ reaction scheme 3]
The compound 5- (4-bromo-3, 5-dimethylphenyl) -5H-dibenzo [ b, f ] azepine (0.3g,0.8mmol) was charged in a two-necked flask, stoppered with serum, dried Tetrahydrofuran (THF) (8mL,0.1M) was added through the side port, and the system was cooled to-78 ℃ with an acetone bath. N-butyllithium (0.48mL,1.8mmol) was slowly added with a plastic needle under nitrogen to form an orange solution, and the acetone bath was maintained for 1 hour. Then, dry Dimethylformamide (DMF) (0.18g,2.4mmol) was added by syringe under nitrogen atmosphere, and the acetone bath was maintained for 1 hour, and the reaction was carried out overnight. After the reaction was completed, water was added and the excess alkali was neutralized with an aqueous hydrochloric acid solution. Extracted 3 times with ethyl acetate and concentrated by rotation. Then, the product was purified by column chromatography (eluent was ethyl acetate/n-hexane 1/19, v/v) to obtain intermediate I-3(0.14g, yield 53.3%) as a yellow solid.
1H NMR(500MHz,CDCl3,δ):10.28(s,1H),7.51(t,J＝7.5Hz,2H),7.44(d,J＝8.0Hz,4H),7.38(t,J＝7.5Hz,2H),6.85(s,2H),5.91(s,2H),2.37(s,6H).13C NMR(125MHz,CDCl3,δ):190.76,151.93,143.82,141.45,135.72,130.45,130.32,129.83,129.48,127.57,123.53,112.27,21.42.
Synthesis example 4: synthesis of intermediate I-4(2, 6-dimethyl-4- (10H-spiro [ [ pyridine-9, 9 '-fluorene ] -10-yl ] benzaldehyde) (2,6-dimethyl-4- (10H-spiro [ acridine-9,9' -fluoro ] -10-yl) benzaldehyde) ("2, 6-dimethyl-4-")
[ reaction scheme 4]
The compound 10- (4-bromo-3, 5-dimethylphenyl) -10H-spiro [ acridine-9,9' -fluorene ] (1g,1.9mmol) was added to a two-necked flask, stoppered with serum, and dried Tetrahydrofuran (THF) (24mL,0.08M) was added via the side port, and the system was cooled to-78 ℃ with an acetone bath; n-butyllithium (1.16mL,2.9mmol) was slowly added with a plastic needle under nitrogen to form an orange solution, and the acetone bath was maintained for 1 hour. Then, dry Dimethylformamide (DMF) (0.43g,5.7mmol) was added by syringe under nitrogen atmosphere, and the acetone bath was maintained for 1 hour, and the reaction was carried out overnight. After the reaction was complete, water was added and excess base was neutralized with aqueous hydrochloric acid. Extracted 3 times with ethyl acetate and concentrated by rotation. Then, the product was purified by column chromatography (eluent was ethyl acetate/n-hexane 1/19, v/v) to obtain intermediate I-4(0.61g, yield 67.2%) as a yellow solid.
1H NMR(500MHz,CDCl3,δ):10.72(s,1H),7.77(d,J＝7.5Hz,2H),7.38-7.33(m,4H),7.23-7.21(m,4H),6.90(t,J＝7.5Hz,2H),6.55(t,J＝7.5Hz,2H),6.38(d,J＝7.5Hz,2H),6.34(d,J＝7.5Hz,2H),2.72(s,6H).13C NMR(125MHz,CDCl3,δ):192.87,156.52,144.96,144.44,140.59,139.19,132.40,132.13,128.37,127.96,127.62,127.23,125.72,124.80,120.86,119.91,114.46,20.67.
Synthesis example 5: synthesis of intermediate I-5(4- (diphenylamino) -2,6-dimethylbenzaldehyde)
[ reaction scheme 5]
The compound 4-bromo-3, 5-dimethyl-N, N-diphenylaniline (1g,2.8mmol) was added to a two-necked flask, stoppered with serum, and dried Tetrahydrofuran (THF) (28mL,0.1M) was added via the side port, and the system was cooled to-78 ℃ with an acetone bath; n-butyllithium (1.7mL,4.3mmol) was slowly added with a plastic needle under nitrogen to form an orange solution, and the acetone bath was maintained for 1 hour. Then, dry Dimethylformamide (DMF) (0.64g,8.7mmol) was added by syringe under nitrogen atmosphere, and the acetone bath was maintained for 1 hour, and the reaction was carried out overnight. After the reaction was completed, water was added and the excess alkali was neutralized with an aqueous hydrochloric acid solution. Extracted 3 times with ethyl acetate and concentrated by rotation. Then, the product was purified by column chromatography (eluent was ethyl acetate/n-hexane 1/19, v/v) to obtain intermediate I-5(0.66g, yield 77.4%) as a pale yellow solid.
1H NMR(500MHz,CDCl3,δ):10.39(s,1H),7.31(t,J＝8.0Hz,4H),7.15-7.12(m,6H),6.58(s,2H),2.47(s,6H).13C NMR(125MHz,CDCl3,δ):191.18,151.60,146.22,143.61,129.58,126.26,125.39,124.76,120.27,21.10.
Synthesis example 6: synthesis of intermediate I-6(4- (bis (4- (tert-butyl) phenyl) amino) -2,6-dimethylbenzaldehyde)
[ reaction scheme 6]
The compound 4-bromo-N, N-bis (4- (tert-butyl) phenyl) -3, 5-dimethylaniline (0.5g,1.1mmol) was added to a two-necked flask, stoppered with serum, and dried Tetrahydrofuran (THF) (11mL,0.1M) was added via the side port, and the system was cooled to-78 ℃ with an acetone bath; n-butyllithium (0.6mL,1.6mmol) was slowly added with a plastic needle under nitrogen to form an orange solution, and the acetone bath was maintained for 1 hour. Then, dry Dimethylformamide (DMF) (0.2g,3.2mmol) was added by syringe under nitrogen, and the acetone bath was maintained for 1 hour, and the reaction was carried out overnight. After the reaction was completed, water was added and the excess alkali was neutralized with an aqueous hydrochloric acid solution. Extracted 3 times with ethyl acetate and concentrated by rotation. Then, the product was purified by column chromatography (eluent was ethyl acetate/n-hexane 1/19, v/v) to obtain intermediate I-6(0.4g, yield 88.0%) as a yellow solid.
1H NMR(500MHz,CDCl3,δ):10.38(s,1H),7.31(d,J＝8.4Hz,4H),7.05(d,J＝8.4Hz,4H),6.55(s,2H),2.48(s,6H),1.32(s,18H).13C NMR(125MHz,CDCl3,δ):190.98,151.90,147.79,143.61,143.28,126.40,125.89,124.64,119.15,34.44,31.37,21.19.
Synthesis example 7: synthesis of intermediate I-7(4- (diphenylamino) -benzaldehyde)
[ reaction scheme 7]
Trianiline (2g,8.2mmol) was added to a two-necked flask, dry Dimethylformamide (DMF) (12mL,0.4M) was added via syringe, and the mixture was pumped three times and the system was cooled to 0 ℃. Phosphorus oxychloride (6.3g,40.8mmol) was added slowly with a plastic needle under nitrogen, the ice bath was removed, and after returning to room temperature, it was heated at 45 ℃ for three hours. After the reaction was completed, a large amount of ice water was added to terminate the reaction, and a yellow solid precipitate was collected with a ceramic funnel. Then, it was purified by column chromatography (eluent: ethyl acetate/n-hexane 1/19, v/v) to obtain intermediate I-7(1.98g, yield 88.8%) as a yellow solid.
1H NMR(500MHz,CDCl3,δ):10.39(s,1H),7.31(t,J＝8.0Hz,4H),7.15-7.12(m,6H),6.58(s,2H),2.47(s,6H).13C NMR(125MHz,CDCl3,δ):191.18,151.60,146.22,143.61,129.58,126.26,125.39,124.76,120.27,21.10.
[ Synthesis of Final Compound ]
Synthesis example 8: synthesis of the compound 4- (4- (9H-carbazol-9-yl) -2,6-dimethylphenyl) -2,6-diphenylpyridine-3, 5-dicyano (4- (4- (9H-carbazol-9-yl) -2, 6-dimethyphenyl) -2,6-diphenylpyridine-3,5-dicarbonitrile, CzmPPC)
[ reaction scheme 8]
Intermediate I-7(0.67g,2.2mmol), benzoylacetic acidNitrile (0.81g,5.6mmol), ammonium acetate (0.43g,5.6mmol) were added to a two-necked flask in the presence of acetic acid (6.7mL), heated to 110 deg.C and refluxed for 12 hours. After the reaction was completed, the reaction mixture was returned to room temperature, and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (1.5g,6.6mmol) was added to a two-necked flask, heated to 110 ℃ and refluxed for 2 hours to effect oxidation. And returning to room temperature after the reaction is finished, pumping, filtering, washing off redundant acetic acid by water, and removing the solvent and the water in high vacuum to obtain a crude product. Purification via column chromatography gave the product CzmPPC as a white solid (0.69g, 57.2% overall yield). Finally, a sublimator is used for high vacuum (5 multiplied by 10)-6torr) the product was refined at a sublimation temperature of 240 ℃.
1H NMR(500MHz,CDCl3,δ):8.19-8.15(m,6H),7.62-7.61(m,6H),7.55(d,J＝8.0Hz,2H),7.51(s,2H),7.46(t,J＝8.0Hz,2H),7.31(t,J＝7.5Hz,2H),2.31(s,6H).13C NMR(125MHz,CDCl3,δ):163.12,160.71,140.56,139.36,137.12,136.06,132.50,131.68,129.52,128.91,126.75,126.04,123.50,120.28,120.15,115.05,110.01,106.45,20.29.HRMS(FD)m/z:[M+]calcd.for C39H26N4,550.2152；found,550.2151.Anal.calcd.for C39H26N4:C 85.07,H 4.76,N 10.17found:C85.17,H 4.51,N 10.03.
Synthesis example 9: synthesis of the Compound 4- (4- (3,6-di-tert-butyl-9H-carbazol-9-yl) -2,6-dimethylphenyl) -2,6-diphenylpyridine-3, 5-dicyano (4- (4- (3,6-di-tert-butyl-9H-carbazol-9-yl) -2,6-dimethylphenyl) -2, 6-dimethylphenylpyridine-3, 5-dicarbonitrile, tCzmPPC)
[ reaction scheme 9]
Intermediate I-2(0.2g,0.5mmol), benzoylacetonitrile (0.18g,1.2mmol), ammonium acetate (0.11g,1.5mmol) were added to a two-necked flask in the presence of acetic acid (5mL), heated to 110 deg.C and refluxed for 12 hours. After the reaction was completed, the reaction mixture was returned to room temperature, and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (0.34g,1.5mmol) was added to a two-necked flask, heated to 110 ℃ and refluxed for 2 hoursTo perform an oxidation reaction. And returning to room temperature after the reaction is finished, performing suction filtration, washing off redundant acetic acid by water, and removing the solvent and the water in high vacuum to obtain a crude product. Purification was performed via column chromatography to give the product, tCzmPPC (0.23g, 68.1% overall yield). Finally, a sublimator is used for high vacuum (5 multiplied by 10)-6torr) the product was refined at a sublimation temperature of 265 ℃.
1H NMR(500MHz,CDCl3,δ):8.15-8.13(m,6H),7.60(m,6H),7.48(m,6H),2.27(s,6H),1.46(s,18H).13C NMR(125MHz,CDCl3,δ):163.10,160.84,143.10,139.89,138.89,136.92,136.11,131.90,131.65,129.53,128.91,126.24,123.69,123.54,116.20,115.06,109.49,106.57,34.73,31.99,20.29.HRMS(FD)m/z:[M+]calcd.for C47H42N4,662.3404；found,662.3405.Anal.calcd.for C47H42N4:C 85.16,H 6.39,N 8.45found:C 85.56,H 5.98,N 8.51.
Synthesis example 10: synthesis of the compound 4- (4- (5H-dibenzo [ b, f ] azepine-5-yl) -2,6-dimethylphenyl) -2,6-diphenylpyridine-3, 5-dicyano (4- (4- (5H-dibenz [ b, f ] azepin-5-yl) -2, 6-dimethyphenyl) -2,6-diphenylpyridine-3,5-dicarbonitrile, DBAZmPP)
[ reaction scheme 10]
Intermediate I-3(0.2g,0.6mmol), benzoylacetonitrile (0.22g,1.5mmol), and ammonium acetate (0.14g,1.8mmol) were added to a two-necked flask in the presence of acetic acid (5.5mL), heated to 110 deg.C, and refluxed for 12 hours. After the reaction was completed, the reaction mixture was returned to room temperature, and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (0.41g,1.8mmol) was added to a two-necked flask, and the mixture was heated to 110 ℃ to conduct oxidation for 2 hours. And returning to room temperature after the reaction is finished, performing suction filtration, washing off redundant acetic acid by water, and removing the solvent and the water in high vacuum to obtain a crude product. Purification was performed via column chromatography to give DBAZmPPC as a yellow product (0.21g, total yield 60.3%). Finally, a sublimator is used for high vacuum (5 multiplied by 10)-6torr) the product was refined, sublimation temperatureThe degree was 260 ℃.
1H NMR(500MHz,CDCl3,δ):8.05(d,J＝7.5Hz,4H),7.54-7.52(m,8H),7.49(t,J＝8.0Hz,2H),7.44(d,J＝7.5Hz,2H),7.35(t,J＝7.5Hz,2H),6.87(s,2H),6.11(s,2H),1.92(s,6H).13C NMR(125MHz,CDCl3,δ):162.75,162.23,149.75,142.44,136.36,136.30,135.13,131.27,130.67,130.21,130.20,129.60,129.45,128.74,127.11,123.09,115.44,111.51,107.58,20.48.HRMS(FD)m/z:[M+]calcd.for C41H28N4,576.2309；found,576.2303.Anal.calcd.for C41H28N4:C 85.39,H4.89,N 9.72found:C 85.23,H 4.66,N 9.70.
Synthesis example 11: synthesis of the compound 4- (2,6-dimethyl-4- (10H-spiro [ [ pyridine-9, 9 '-fluorene ] -10-yl) phenyl) -2,6-diphenylpyridine-3, 5-dicyano (4- (2,6-dimethyl-4- (10H-spiro [ acid-9, 9' -fluoro ] -10-yl) phenyl) -2,6-diphenylpyridine-3,5-dicarbonitrile, SAcmPPC)
[ reaction scheme 11]
Intermediate I-4(0.2g,0.4mmol), benzoylacetonitrile (0.16g,1.1mmol), ammonium acetate (0.1g,1.3mmol) were added to a two-necked flask in acetic acid (5.5mL) as the solvent, heated to 110 deg.C and refluxed for 12 hours. After the reaction was completed, the reaction mixture was returned to room temperature, and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (0.27g,1.2mmol) was added to a two-necked flask, heated to 110 ℃ and refluxed for 2 hours to effect oxidation. And returning to room temperature after the reaction is finished, pumping, filtering, washing off redundant acetic acid by water, and removing the solvent and the water in high vacuum to obtain a crude product. Purification was performed via column chromatography to give the yellow product SAcmPPC (0.15g, 51.4% overall yield). Finally, a sublimator is used for high vacuum (5 multiplied by 10)-6torr) the product was refined with a sublimation temperature of 310 ℃.
1H NMR(500MHz,CDCl3,δ):8.19(d,J＝7.5Hz,4H),7.79(d,J＝7.5Hz,2H),7.62-7.61(m,6H),7.43-7.42(m,4H),7.37(t,J＝7.5Hz,2H),7.26(d,J＝7.5Hz,2H),6.98(t,J＝7.5Hz,2H),6.58(t,J＝7.5Hz,2H),6.49(d,J＝8.5Hz,2H),6.41(d,J＝8.0Hz,2H),2.33(s,6H).13C NMR(125MHz,CDCl3,δ):163.09,160.88,156.52,142.69,140.93,139.21,138.48,136.07,133.97,131.74,131.10,129.55,129.53,128.95,128.35,127.73,127.57,127.48,125.77,124.75,120.76,119.88,115.06,114.67,106.37,20.27.HRMS(FD)m/z:[M+]calcd.for C52H34N4,714.2778；found,714.2783.Anal.calcd.for C52H34N4:C 87.37,H 4.79,N 7.84found:C 87.56,H 4.38,N 7.91.
Synthesis example 12: synthesis of 4- (4- (diphenylamino) -2,6-dimethylphenyl) -2,6-diphenylpyridine-3, 5-dicyano (4- (4- (diphenylamino) -2,6-dimethylphenyl) -2,6-diphenylpyridine-3,5-dicarbonitrile, TPAmPPC)
[ reaction scheme 12]
Intermediate I-5(0.2g,0.7mmol), benzoylacetonitrile (0.24g,1.7mmol), and ammonium acetate (0.15g,2.0mmol) were added to a two-necked flask in the presence of acetic acid (6mL), heated to 110 deg.C, and refluxed for 12 hours. After the reaction was completed, the reaction mixture was returned to room temperature, and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (0.48g,2.1mmol) was added to a two-necked flask, heated to 110 ℃ and refluxed for 2 hours to effect oxidation. And returning to room temperature after the reaction is finished, pumping, filtering, washing off redundant acetic acid by water, and removing the solvent and the water in high vacuum to obtain a crude product. Purification was performed via column chromatography to give the product TPAmPPC (0.21g, 54.1% overall yield). Finally, a sublimator is used for high vacuum (5 multiplied by 10)-6torr) and a sublimation temperature of 230 ℃.
1H NMR(500MHz,CDCl3,δ):8.10(d,J＝7.5Hz,4H),7.57-7.56(m,6H),7.29(t,J＝7.5Hz,4H),7.16(d,J＝8.0Hz,4H),7.06(t,J＝7.5Hz,2H),6.87(s,2H),2.04(s,6H).13C NMR(125MHz,CDCl3,δ):162.85,161.70,149.20,147.18,136.21,135.84,131.41,129.45,129.38,128.78,126.68,125.36,123.54,121.41,115.27,107.11,20.21.HRMS(FD)m/z:[M+]calcd.for C39H28N4,552.2309；found,552.2313.Anal.calcd.for C39H28N4:C 84.76,H 5.11,N 10.14found:C 85.09,H4.78,N 10.08.
Synthesis example 13: synthesis of 4- (4- (Bis (4- (tert-butyl) phenyl) amino) -2,6-dimethylphenyl) -2,6-diphenylpyridine-3, 5-dicyano (4- (4- (tert-butyl) phenyl) amino) -2,6-dimethylphenyl) -2,6-diphenylpyridine-3,5-dicarbonitrile, tTPAmPPC)
[ reaction scheme 13]
I-6(0.4g,0.9mmol), benzoylacetonitrile (0.4g,2.4mmol), ammonium acetate (0.2g,2.9mmol) were added to a two-necked flask in acetic acid (15mL) as a solvent, heated to 110 deg.C and refluxed for 12 hours. After the reaction was completed, the reaction mixture was returned to room temperature, and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (0.61g,2.7mmol) was added to a two-necked flask, heated to 110 ℃ and refluxed for 2 hours to effect oxidation. And returning to room temperature after the reaction is finished, pumping, filtering, washing off redundant acetic acid by water, and removing the solvent and the water in high vacuum to obtain a crude product. Purification was performed via column chromatography to give the product tpamppc (0.34g, total yield 57.0%). Finally, a sublimator is used for high vacuum (5 multiplied by 10)-6torr) the product was refined at a sublimation temperature of 260 ℃.
1H NMR(500MHz,CDCl3,δ):8.10(d,J＝7.2Hz,4H),7.57-7.56(m,6H),7.29(d,J＝7.8Hz,4H),7.09(d,J＝7.9Hz,4H),6.85(s,2H),2.05(s,6H),1.32(s,18H).13C NMR(125MHz,CDCl3,δ):162.83,161.95,149.55,146.31,144.47,136.30,135.64,131.37,129.49,128.80,126.17,125.97,124.90,120.78,115.34,34.33,31.42,20.27.HRMS(EI)m/z:[M+]calcd.for C47H44N4,664.3566；found,664.3564.Anal.calcd.for C47H44N4:C 84.90,H 6.67,N 8.43found:C 84.78,H 6.55,N 8.33.
Synthesis of comparative example 1: synthesis of 4- (4- (diphenylamino) phenyl) -2,6-diphenylpyridine-3, 5-dicyano (4- (4- (diphenylamino) phenyl) -2,6-diphenylpyridine-3,5-dicarbonitrile, TPAPPC)
[ reaction scheme 14]
Intermediate I-7(1.0g,3.7mmol), benzoylacetonitrile (1.2g,8mmol), and ammonium acetate (1.3g,16.5mmol) were added to a two-necked flask in the presence of acetic acid (29mL), heated to 110 deg.C and refluxed for 12 hours. After the reaction was completed, the reaction mixture was returned to room temperature, and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (2.5g,11.1mmol) was added to a two-necked flask in the presence of acetic acid (20mL) as a solvent, and the mixture was heated to 110 ℃ and refluxed for 2 hours to effect oxidation. And returning to room temperature after the reaction is finished, pumping, filtering, washing off redundant acetic acid by water, and removing the solvent and the water in high vacuum to obtain a crude product. Purification was performed via column chromatography to give TPAPPC (1.5g, total yield 78.0%) as a yellow product. Finally, a sublimator is used for high vacuum (5 multiplied by 10)-6torr) the product was refined at a sublimation temperature of 240 ℃.
1H NMR(500MHz,CDCl3,δ):8.03(d,J＝7.3Hz,6H),7.55-7.54(m,2H),7.48(d,J＝8.6Hz,4H),7.32(t,J＝7.6Hz,4H),7.21(d,J＝7.8Hz,4H),7.13(dd,J＝13.8,7.9Hz,4H).13C NMR(125MHz,CDCl3,δ):163.55,155.96,150.44,146.52,136.60,131.21,130.34,129.64,129.55,128.71,126.09,124.91,124.55,120.12,116.41,105.57.HRMS(EI)m/z:[M+]calcd.for C37H24N4,524.2001；found,524.2006.Anal.calcd.for C37H24N4:C 84.71,H 4.61,N 10.68found:C 84.64,H4.43,N 10.59.
In this example, Nuclear Magnetic Resonance (NMR) spectra of the above compounds were measured by a spectrometer (Varian Mercury 500). Hydrogen nuclear magnetic resonance spectrum (1H NMR) in CDCl3For the standard, the chemical shift (chemical shift) was defined as 7.24ppm, the symbol s represents a singlet (singlet), d represents a doublet (doubtet), t represents a triplet (triplet), and m represents a multiplet (multiplet)Dd denotes a doublet of doublets (doublets) and the coupling constant (coupling constant) is in Hz.13Chemical shifts of the C NMR spectrum in CDCl3As a standard, the chemical shift was 77.0 ppm. High resolution mass spectra were determined using a JEOL AccuTOF GCx HRGCMS or JEOL JMS-700HRMS mass spectrometer. The weight percentages of carbon, hydrogen, nitrogen and sulfur in the sample were determined by an Elemental analyzer (elementary analyzer) which is a fully automatic Elemental analyzer, vario EL III CHN-OS Rapid (elmendor).
[ evaluation of Properties of Compounds ]
[ photophysical Properties ]
[ ultraviolet-visible absorption Spectroscopy and photoexcitation Spectroscopy ]
The compounds of Synthesis examples 8 to 13 and Synthesis comparative example 1 were placed in 10-5M in a toluene solution, calibration was performed in a quartz sample cell, and ultraviolet-visible absorption (UV-vis absorption) spectra of the compounds of synthesis examples 8 to 13 and synthesis comparative example 1 were measured by a spectrophotometer (spectrophotometer) Hitach U-3300, and Photoexcitation (PL) spectra of the compounds of synthesis examples 8 to 13 and synthesis comparative example 1 were measured by a fluorescence spectrometer (fluorescence spectrophotometer) Hitach F-7000.
[ ultraviolet photoelectron spectroscopy ]
In the present example, electron dissociation energies of the compounds of synthesis examples 8 to 13 and synthesis comparative example 1 in a thin film state were measured using a photoelectron spectrometer (photoelectron spectrometer) to obtain an ultraviolet photoelectron spectrum. Specifically, each sample was formed as an undoped film and set on a glass substrate, and the surface of the film was irradiated with ultraviolet light. Because of the small attraction between the valence electrons and the nuclei of the surface layer of the compound, the valence electrons are ejected away from the surface after absorbing high energy and form negatively charged O with oxygen2 -The initial energy at which electrons are accelerated into the detector under an electric field and begin to be detected by the instrument is the HOMO level of the compound in electron volts (eV). The energy difference (energy gap, E) from the ground state to the singlet excited state is calculated from the initial value (onset) of the absorption spectrumg) Then is further prepared byHOMO and EgThe LUMO energy level of the compound was calculated.
The results of synthesizing the ultraviolet-visible absorption spectrum, the photoexcitation spectrum, and the ultraviolet photoelectron spectrum of the compounds of examples 8 to 13 and comparative example 1 are shown in table 3 below. Fig. 4 is an ultraviolet-visible absorption (UV-vis absorbance) spectrum of the compounds of synthesis examples 8 to 13 and synthesis comparative example 1. Fig. 5 is a photoexcitation emission spectrum of the compounds of synthesis examples 8 to 13 and synthesis comparative example 1.
[ Table 3]
| Synthesis examples | λabs(nm) | λTol(nm) | Eg(eV) | HOMO(eV) | LUMO(eV) |
| CzmPPC | 292 | 482 | 3.07 | -5.82 | -2.75 |
| tCzmPPC | 298 | 502 | 2.92 | -5.72 | -2.80 |
| DBAZmPPC | 288 | 526 | 2.73 | -5.72 | -2.99 |
| SAcmPPC | 296 | 534 | 2.68 | -5.61 | -2.93 |
| TPAmPPC | 302 | 544 | 2.61 | -5.69 | -3.08 |
| tTPAmPPC | 304 | 564 | 2.53 | -5.60 | -3.07 |
| Comparative example of Synthesis | λabs(nm) | λTol(nm) | Eg(eV) | HOMO(eV) | LUMO(eV) |
| TPAPPC | 290 | 503 | 2.64 | -5.76 | -3.12 |
λabs: absorption wavelength in toluene
λTol: emission wavelength in toluene
As can be seen from the results shown in Table 3 and FIGS. 4 to 5, the HOMO level of the cyanopyridine-containing compounds of the present invention is in the range of-5.82 eV to-5.60 eV, and the LUMO level is in the range of-3.12 eV to-2.75 eV. In addition, the light emission of the cyanopyridine-containing compound of the present invention covers blue light, green light to yellow light, and the light emission wavelength is between 482nm and 564 nm. That is, with the nitrogen-containing group (R) at the para-position on the phenyl group3) The cyanopyridine-containing compounds of the present invention have different light emission colors. That is, the cyanopyridine compound of the present invention satisfies the requirement of multiple optical activities. Thus, the present invention can be achieved by changing the nitrogen-containing group (R) of the cyanopyridine-containing compound3) The structure of (a) to control the color of emission of cyanopyridine-containing compounds.
[ Room temperature fluorescence Spectroscopy and Low temperature phosphorescence Spectroscopy ]
The compounds of synthesis examples 8 to 13 and synthesis comparative example 1 were doped at 10 wt% in a host material, mCPCN, which was evaporated on a quartz plate at 30nm to form a thin film, and placed in a transparent quartz tube. The room temperature fluorescence spectrum and the low temperature phosphorescence spectrum were measured by a fluorescence spectrometer (fluorescence spectrophotometer) Hitach F-7000. In this example, the measurement temperature of the room temperature fluorescence spectrum is 298K, and the measurement temperature of the low temperature phosphorescence spectrum is 77K. Calculation of E from the starting wavelength of the fluorescence SpectroscopySCalculating E as the starting wavelength of the phosphorescence spectrumTThe two are subtracted to obtain Delta ESTIn electron volts (eV). ChamberThe results of the warm fluorescence spectrum and the low temperature phosphorescence spectrum are shown in table 4 below.
[ measurement of luminescence quantum efficiency ]
The compounds of synthesis examples 8 to 13 and synthesis comparative example 1 were doped with 10 wt% of a host emitter mCPCN, and the above materials were deposited on a quartz plate to form a thin film by 30 nm. The calibration was performed with a blank quartz plate, and then the luminescent quantum efficiency (PLQY) of the film sample on the quartz plate was measured under nitrogen using an integrating sphere (integrating sphere).
[ Table 4]
| Synthesis examples | ES(eV) | ET(eV) | ΔEST(eV) | ΦPLQY(％) |
| CzmPPC | 2.95 | 2.68 | 0.27 | 92 |
| tCzmPPC | 2.82 | 2.70 | 0.12 | 97 |
| DBAZmPPC | 2.80 | 2.78 | 0.02 | 24 |
| SAcmPPC | 2.73 | 2.68 | 0.05 | 100 |
| TPAmPPC | 2.69 | 2.67 | 0.02 | 100 |
| tTPAmPPC | 2.60 | 2.58 | 0.02 | 79 |
| Comparative example of Synthesis | ES(eV) | ET(eV) | ΔEST(eV) | ΦPLQY(％) |
| TPAPPC | 2.73 | 2.52 | 0.21 | 100 |
FIG. 6 shows the room temperature fluorescence spectrum and the low temperature phosphorescence spectrum of CZmPPC according to example of the present invention. Fig. 7 shows a room temperature fluorescence spectrum and a low temperature phosphorescence spectrum of TPAmPPC according to an embodiment of the present invention. FIG. 8 shows the room temperature fluorescence spectrum and the low temperature phosphorescence spectrum of tCzmPPPC according to example of the present invention. FIG. 9 shows a room temperature fluorescence spectrum and a low temperature phosphorescence spectrum of TPAPPC according to an embodiment of the present invention.
As shown in fig. 6 to 9 and table 4. Delta E of cyanopyridine Compound of the present inventionSTBetween 0.02eV and 0.27eV, which is in accordance with the characteristics (Delta E) of the thermally activated delayed fluorescence moleculeST<0.3 eV). When Δ ESTSmaller, molecules tend to return from the triplet excited state to the singlet excited state more readily and emit delayed fluorescence.
In addition, as shown in table 4, PLQY of the cyanopyridine-containing compounds CzmPPC, tCzmPPC, TPAmPPC, sacmpc, TPAmPPC in the film was 92%, 97%, 100%, 79%, respectively, and excellent performance of these cyanopyridine-containing compounds in the film was expected. The pyridine-3, 5-dicyano has good molecular structure rigidity, and the steric barrier between the dimethyl on the phenyl (connecting group) and the dicyano on the pyridine can avoid non-radiative decline of molecular motion and the like, so that the cyanopyridine-containing compound can reach nearly 100% PLQY, and the cyanopyridine-containing compound has the potential of a high-efficiency TADF material and is beneficial to being applied to a light-emitting component.
[ test for Heat stability Properties ]
In the evaporation process of an OLED device, it is necessary to ensure that the compound does not decompose at high temperature and that a thin film of amorphous phase (amorphous) is formed to avoid crystallization hindering the transport of charges. In addition, during operation of the device, the excitons are exposed to a charged environment, and thus the compound has a high Bond Dissociation Energy (BDE).
In this example, thermogravimetric analysis was usedTGA (Thermogravimetric analysis, TGA) (Mettler-Toledo) company) was measured for the change in weight of a substance with respect to Temperature at a Temperature rising rate of 10 ℃ per minute under nitrogen to obtain thermal cracking temperatures (T) of the compounds of Synthesis examples 8 to 13 and Synthesis comparative example 1d) Wherein the thermal cracking temperature is defined as the temperature at which 5% by weight is lost. The thermal cracking temperatures of the compounds of synthesis examples 8 to 13 and synthesis comparative example 1 are shown in table 5 below.
[ measurement of delayed fluorescence Property ]
The compounds of Synthesis examples 8 to 13 and Synthesis example 1 were doped in 10 wt% respectively in a host material mCPCN and the above materials were evaporated on a quartz plate, an instantaneous light excitation spectrum was measured by an instantaneous light excitation spectrometer (Transient PL) Edinburgh FLS-S2S2-stm, and an instantaneous Fluorescence lifetime (τ) was calculated from the program F980p) Delayed Fluorescence lifetime (Delayed Fluorescence lifetime, tau)d) Instantaneous fluorescence emission quantum efficiency (phi)prompt) And delayed fluorescence emission quantum efficiency (phi)delayed) The results are shown in Table 5 below.
[ Table 5]
| Synthesis examples | Td(℃) | τp(ns) | τd(μs) | Φprompt(％) | Φdelayed(％) |
| CzmPPC | 363 | 42 | 462 | 19 | 73 |
| tCzmPPC | 374 | 54 | 87 | 25 | 72 |
| DBAZmPPC | 371 | 15 | 0.1 | 5 | 19 |
| |
400 | 99 | 72 | 16 | 84 |
| TPAmPPC | 336 | 33 | 3 | 9 | 91 |
| tTPAmPPC | 370 | 14 | 2 | 3 | 76 |
| Comparative example of Synthesis | Td(℃) | τp(ns) | τd(μs) | Φprompt(％) | Φdelayed(％) |
| TPAPPC | 380 | 10 | 134 | 5 | 95 |
As is clear from the results in table 5, the thermal cracking temperature of the cyanopyridine-containing compound of the present invention is 336 to 400 ℃, and the thermal stability is excellent, so that it is ensured that cracking does not occur during the evaporation process.
In addition, the transient fluorescence lifetime (. tau.) of the cyanopyridine-containing compounds of the present inventionp) Are all less than 100 nanoseconds (ns), which represents the rapid light emission of the singlet excited state returning to the ground state, which is an important indicator of the delayed fluorescence property with thermal activation. Delayed fluorescence lifetime (τ) of cyanopyridine-containing compounds of the inventiond) Short, and delayed fluorescence emission quantum efficiency (phi)delayed) High in fluorescence and excellent in thermal activation delayed fluorescence property. The synthesized TPAPPC of comparative example has larger Delta E because the electron clouds of HOMO and LUMO are partially overlapped due to the lack of steric hindrance at the ortho-position of the phenyl groupSTResulting in a long delayed fluorescence lifetime of TPAPPC(134 microseconds (μ s)).
[ production of organic light-emitting diode ]
Experimental example 1
An organic light emitting diode was fabricated using 9- (3- (9H-carbazol-9-yl) phenyl) -9H-carbazolyl-3-carbonitrile (9- (3- (9H-carbazol-9-yl) phenyl) -9H-carbazole-3-carbonitrile, mCPCN) as a host light emitting material and the compound CzmPPC obtained in synthesis example 8 as a guest light emitting material (i.e., dopant).
Specifically, the manufacturing process of the organic light emitting diode is as follows: first, molybdenum trioxide (MoO) is deposited on an ITO glass substrate as an anode3) To form a hole injection layer. Then, deposit di- [4- (N, N-di (p-tolyl) amino) phenyl group on the hole injection layer]Cyclohexane, (1,1-bis [4- [ N, N' -di (p-tolyl) amino)]phenyl]cyclohexane, TAPC) to form a hole transport layer. Then, 1,3-bis (9-carbazolyl) benzene (1,3-bis (9-carbazolyl) benzene, mCP) was deposited on the hole transport layer to form an exciton blocking layer. Next, a host light emitting material mCPCN (20nm) doped with 10% of the compound CzmPPC was deposited to form a light emitting layer. Then, tri- [3- (3-pyridyl) 2,4, 6-trimethylphenyl is deposited on the light-emitting layer]Borane (3, 3' - [ borylidynylris (2,4, 6-trimethy-3, 1-phenylene)]tris[pyridine]3TPYMB) (50nm) to form an electron transport layer. Then, LiF (electron injection layer) (0.5nm) and Al were sequentially deposited on the electron transport layer to form a cathode. Thus, the organic light emitting diode of the present experimental example was manufactured. In this example, the cyanopyridine-containing compound CzmPPC of the present invention was used as an dopant.
The organic light emitting diode has the following structure: ITO/MoO3(1nm)/TAPC(50nm)/mCP(10nm)/mCPCN:CzmPPC(10wt％)(20nm)/3TPYMB(50nm)/LiF(0.5nm)/Al(100nm)。
Experimental example 2
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that the compound tCzmPPC obtained in synthesis example 9 was used as a dopant for the light emitting layer.
Experimental example 3
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that the compound DBAZmPPC obtained in synthesis example 10 was used as a dopant for the light emitting layer.
Experimental example 4
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that the compound sacppc obtained in synthesis example 11 was used as a dopant of the light emitting layer.
Experimental example 5
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that the compound TPAmPPC obtained in synthesis example 12 was used as a dopant for the light emitting layer.
Experimental example 6
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that the compound tpamppc obtained in synthesis example 13 was used as a dopant for the light emitting layer.
Comparative example 1
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that TPAPPC, the compound obtained in synthetic comparative example 1, was used as a dopant for the light emitting layer.
Comparative example 2
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that the compound TPAsPPC was used as a dopant of the light emitting layer.
Comparative example 3
An organic light emitting diode was formed using a method similar to that of experimental example 1, except that the compound tCzmPMC was used as a dopant of the light emitting layer. In the structure of the compound tCzmPMC, the position 2 and 6 (R) of the pyridyl group in the core structure3) Introducing a firstAnd (4) a base.
[ evaluation of efficacy of organic light emitting diode ]
Fig. 10 is a photoexcitation emission spectrum of the organic light-emitting diodes of experimental examples 1 to 6. Table 6 shows the results of testing the performance of the organic light emitting diodes of experimental examples 1 to 6 and comparative examples 1 to 3. In this embodiment, the threshold voltage of the OLED is 1cd m-2The operating voltage of the time. The brightness, external quantum efficiency, luminous efficiency, and power efficiency of the organic light emitting diode are maximum values of the components, respectively. The emission wavelength and the CIE coordinates of the organic light emitting diode are the electroluminescence characteristics with an operating voltage of 8V.
[ Table 6]
As can be seen from fig. 10, the light emission wavelengths of the organic light emitting diodes of experimental examples 1 to 6 can range from sky blue (480nm) to yellow (556 nm). That is, with the nitrogen-containing group (R) at the para-position on the phenyl group3) The cyanopyridine-containing compounds of the present invention have different light emission colors. Thus, the present invention can be achieved by changing the nitrogen-containing group (R) of the cyanopyridine-containing compound3) The structure of the organic light emitting diode is used for regulating and controlling the light emitting color of the organic light emitting diode.
In addition, as can be seen from the results in table 6, the threshold voltages of the organic light emitting diodes of experimental examples 1 to 6 are all 3.0V or less (2.6V to 3.0V). The light emission wavelength of the organic light emitting diode (having the compound CzmPPC as a dopant) of experimental example 1 was 480nm, the maximum external quantum efficiency was 16.1% and the maximum light emission efficiency was 36.8cd a-1Maximum, maximumPower efficiency of 38.5lm W-1. The organic light emitting diode of experimental example 6 (having the compound tpamappc as a dopant) exhibited a light emission wavelength of 556nm, yellow light, a maximum external quantum efficiency of 29.8%, and a maximum light emission efficiency of 91.8cd a-1Maximum power efficiency of 96.1lm W-1。
Among the above examples, the organic light emitting diodes of examples 4 (having the compound sacppc as an dopant) and 5 (having the compound TPAmPPC as an dopant) had more excellent device efficiency performance, and the maximum external quantum efficiencies thereof were 37.6% and 39.8%, respectively, and the maximum light emitting efficiency was 122.8cd a-1And 133.5cd A-1Maximum power efficiency of 128.6lm W-1And 139.8lm W-1Superior efficiency performance to typical TADF materials.
Fig. 11 is a luminance-external quantum efficiency curve of the organic light emitting diodes of experimental example 5, comparative example 1, and comparative example 2.
As can be seen from the results of fig. 11, the organic light emitting diodes of comparative examples 1 and 2 have a higher rate of decrease in external quantum efficiency as the luminance increases, as compared to the organic light emitting diode of experimental example 5. When in high brightness (1000cd m)-2) In the case of (1), the external quantum efficiency of the organic light emitting diode of comparative example 1 was only about 9.6%, which was much lower than that of experimental example 5 (27.0%). This is due to the greater Δ E of the compound TPAPCC of comparative example 1STTherefore, at high current densities, exciton-quenching or exciton-quenching is easily generated, resulting in loss of energy and efficiency. That is, the above results demonstrate that the introduction of two methyl groups at the ortho position of the phenyl group of the linking group (which can generate steric hindrance with the cyano group of the pyridyl group) can reduce the lifetime of delayed fluorescence, improve the efficiency of the light emitting device at high luminance, and thus can be more effectively applied to a display.
Fig. 12 is a luminance-external quantum efficiency curve of the organic light emitting diodes of experimental example 2 and comparative example 3.
Referring to fig. 12 and table 6, the maximum external quantum efficiency, the maximum luminous efficiency, and the maximum power efficiency of the organic light emitting diode of comparative example 3 are respectivelyOnly 3.2%, 4.6cd A-1And 4.2lm W-1Not only far below the efficiency performance of experimental example 2. In addition, the maximum external quantum efficiency of comparative example 3 is less than 5%, that is, the compound tCzmPMC of comparative example 3 does not have the characteristic of "the thermally activated delayed fluorescence molecule can improve the use ratio of the exciton by being transformed", and belongs to the conventional fluorescent material. The above results confirmed that the cyanopyridine-containing compounds of the present invention are present in the positions 2 and 6 (R) of the pyridyl group of the core structure3) The introduction of aromatic groups is important for the thermally activated delayed fluorescence properties and the luminous efficiency of the assembly.
[ component annealing test ]
In this example, the thermal stability of the cyanopyridine-containing compounds of the present invention was further tested via a thermal annealing (thermal annealing) experiment. After the organic light emitting diode is evaporated and packaged in a glove box under the nitrogen environment, the organic light emitting diode is placed on a heating plate. And then, heating at 50 ℃ and 80 ℃ for 20 minutes respectively, standing to return to room temperature after heating, and then carrying out electrical property test on the organic light-emitting diode.
In this example, the annealing test was performed using the organic light emitting diode of experimental example 5 (having the compound TPAmPPC as a dopant), and the results thereof are as follows in table 7.
[ Table 7]
Fig. 13 is a graph of luminance versus external quantum efficiency of the organic light emitting diode of experimental example 5 at different temperatures.
As can be seen from the results of FIG. 13 and Table 7, the OLED of Experimental example 5 exhibits a stability of a certain level even after being heated at 80 deg.C, and has a maximum external quantum efficiency of 29.0% and a maximum luminance of 14459cd m-2. In addition, as the heating temperature increased, the light emitting position and the threshold voltage of the organic light emitting diode of experimental example 5 were not changed, and the light leakage did not occur in the electroluminescence spectrum, which represents that the compound TPAmPPC was used as the light emitting diodeThe organic light-emitting guest material may have good thermal stability.
[ test of lifetime of light-emitting component ]
[ production of organic light-emitting diode ]
Experimental example 7
In this embodiment, the materials for fabricating the organic light emitting diode are in the following order: the anode is ITO, the hole injection layer is 1,4,5,8,9, 12-hexaazatriphenylene hexacarbonitrile (HAT-CN), the hole transport layer is 9,9 '-triphenyl-9H, 9H' -3,3',6',3 '-tricarbazole (9-Phenyl-3,6-bis (9-Phenyl-9Hcarbazol-3-yl) -9H-carbazole, Tris-PCz), the blocking layer is 1,3-bis (9-carbazolyl) benzene (1,3-bis (9-carbazolyl) benzene, mCP), the host material in the light emitting layer is 3,3' -bis (N-carbazolyl) -1,1 '-biphenyl (3, 3' -Di (9H-carbazol-9-yl) -1,1 '-biphenyl, mCBP), the cyanopyridine compound CzmPPC of the present invention is used as a guest material, the hole blocking layer is 2,4,6-tris ([1,1' -biphenyl ] -3-yl) -1,3,5-triazine (2,4,6-tris (biphenyl-3-yl) -1,3,5-triazine, T2T), the electron transport layer is 2,7-Bis ([2,2 '-bipyridine ] -5-yl) triphenylene (2,7-Bis (2, 2' -bipyridine-5-yl) triphenylene, BPy-TP2), the electron injection layer is LiF, and the cathode material is Al.
The organic light emitting diode has the following structure: ITO/HAT-CN (10nm)/Tris-PCz (30nm)/mCP (10nm)/mCBP 10 wt% guest material (30nm)/T2T (10nm)/BPy-TP2(40nm)/LiF (1.0nm)/Al (100 nm).
Experimental example 8
An organic light emitting diode was formed using a method similar to that of experimental example 7, except that the compound tCzmPPC obtained in synthesis example 9 was used as a dopant for the light emitting layer.
Experimental example 9
An organic light emitting diode was formed using a method similar to that of experimental example 7, except that the compound sacppc obtained in synthesis example 11 was used as a dopant of the light emitting layer.
Experimental example 10
An organic light emitting diode was formed using a method similar to that of experimental example 7, except that the compound TPAmPPC obtained in synthesis example 12 was used as a dopant for the light emitting layer.
Experimental example 11
An organic light emitting diode was formed using a method similar to that of experimental example 7, except that the compound tpamappc obtained in synthesis example 13 was used as a dopant for the light emitting layer.
Comparative example 4
An organic light emitting diode was formed using a method similar to that of experimental example 7, except that TPAPPC, the compound obtained in synthetic comparative example 1, was used as a dopant for the light emitting layer.
The half-life test mode of the component is 1000cd m in brightness-2As the initial brightness (L)0＝1000cd m-2) The luminance of the OLED is measured to be reduced to half (L500 cd m)-2) The measurement results of the elapsed time are shown in Table 8 below. Fig. 14 shows the results of the lifetime test of the light emitting devices of experimental example 10, experimental example 11, and comparative example 4.
[ Table 8]
As can be seen from the results of fig. 14 and table 8, the half-life of the device of the organic light emitting diode of experimental example 10 (having the compound TPAmPPC as a dopant) was the longest, reaching 208 hours, and was significantly better than the half-life of the device of the organic light emitting diode of comparative example 4 (having the compound tpapppc as a dopant) (3 hours). This is because the TPAmPPC compound has a short delayed fluorescence lifetime, thereby reducing the time that the material is in an exciton, avoiding the reaction with holes, electrons and excitons in the environment, further avoiding the breakage of non-radiative decay paths or chemical bonds, and greatly improving the stability of the light emitting device.
The cyanopyridine compound of the present invention has excellent heat activated delayed fluorescence characteristic as the guest material of organic light emitting diode component andthe molecular rigidity can shorten the life time of delayed fluorescence by changing the electron-pushing group at the para position of the phenyl and introducing the double methyl group at the ortho position of the phenyl, thereby achieving rapid reverse intersystem crossing (RISC) and 100 percent of luminous quantum efficiency so as to effectively utilize an exciton. In addition, the electroluminescent assembly made of the cyanopyridine compound has assembly efficiency as high as 40% and maximum brightness as high as 15256cd m-2And at high brightness (1000cd m)-2) The external quantum efficiency can still maintain 27.0 percent and meet the specification required by practical application.
In addition, the good stability of the cyanopyridine-containing compounds of the present invention was further demonstrated via annealing assembly tests and lifetime assembly tests, consistent with the long-term operation of the panels.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A cyanopyridine compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the first and second,
Ar1and Ar2May be the same or different and are each independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl;
R1and R2May be the same or different and are each independently substituted or unsubstituted alkyl; and
R3is a nitrogen-containing group.
2. The cyanopyridine-containing compound of claim 1, wherein R3Any one selected from the following structures:
3. the cyanopyridine compound of claim 1, wherein Ar1And Ar2Each independently is any one selected from the following structures:
4. the cyanopyridine-containing compound of claim 1, wherein R1And R2Each independently being methyl, ethyl or propyl.
5. The cyanopyridine-containing compound of claim 1, wherein the cyanopyridine-containing compound is selected from any one of the following structural formulae:
6. an electroluminescent device comprising:
a cathode;
an anode; and
a light-emitting layer disposed between the cathode and the anode, the light-emitting layer comprising the cyanopyridine compound of any one of claims 1-5.
7. The electroluminescent device of claim 6, wherein the light-emitting layer comprises a host light-emitting material and a guest light-emitting material.
8. The electroluminescent device of claim 7, wherein the host luminescent material comprises the cyanopyridine compound.
9. The electroluminescent device of claim 7, wherein the guest emissive material comprises the cyanopyridine-containing compound.
10. The electroluminescent device of claim 6, further comprising at least one auxiliary layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an exciton blocking layer, an electron injection layer, an electron transport layer, and an electron blocking layer.
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| CN113105435A (en) * | 2021-04-13 | 2021-07-13 | 南京益米昇光电科技有限公司 | Thermal activation delayed fluorescence material based on cyanopyridine, preparation method thereof and application thereof in organic electroluminescence |
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