CN108250111A - A kind of amboceptor organic light emission small molecule material and its preparation method and application - Google Patents
A kind of amboceptor organic light emission small molecule material and its preparation method and application Download PDFInfo
- Publication number
- CN108250111A CN108250111A CN201810035059.2A CN201810035059A CN108250111A CN 108250111 A CN108250111 A CN 108250111A CN 201810035059 A CN201810035059 A CN 201810035059A CN 108250111 A CN108250111 A CN 108250111A
- Authority
- CN
- China
- Prior art keywords
- amboceptor
- light emission
- small molecule
- organic light
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 58
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 29
- -1 aromatic amine compounds Chemical class 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical group CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 150000004982 aromatic amines Chemical group 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000000950 dibromo group Chemical group Br* 0.000 claims 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims 1
- 150000002991 phenoxazines Chemical class 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- 238000000859 sublimation Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 90
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 81
- 150000001875 compounds Chemical class 0.000 description 42
- 238000000921 elemental analysis Methods 0.000 description 36
- 239000012074 organic phase Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 239000000284 extract Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000003111 delayed effect Effects 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 229960001866 silicon dioxide Drugs 0.000 description 7
- 238000003809 water extraction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000007725 thermal activation Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BKPDQETYXNGMRE-UHFFFAOYSA-N 1-tert-butyl-9h-carbazole Chemical class N1C2=CC=CC=C2C2=C1C(C(C)(C)C)=CC=C2 BKPDQETYXNGMRE-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- VXGOQVMIGNMUGC-UHFFFAOYSA-N 1-methylacridine Chemical compound C1=CC=C2C=C3C(C)=CC=CC3=NC2=C1 VXGOQVMIGNMUGC-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- JWIPGAFCGUDKEY-UHFFFAOYSA-L O[Cr](Cl)(=O)=O.C1=CC=NC=C1 Chemical compound O[Cr](Cl)(=O)=O.C1=CC=NC=C1 JWIPGAFCGUDKEY-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001644 phenoxazinyl group Chemical class C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of amboceptor organic light emission small molecule materials, are connected to form a kind of novel amboceptor skeleton unit by phenyl ring with carbonyl and sulfuryl, both sides respectively connect a phenyl ring to increase reaction site.The invention also discloses the preparation method and applications of above-mentioned amboceptor organic light emission small molecule material.The luminescent material that the receptor of the present invention is connected can realize that Intramolecular electron transfer acts on, and its bipolar transmission characteristic reduces the unbalanced problem of unipolarity luminescent material carrier, so as to simplify device architecture and improve device performance.The present invention is prepared simply, by a series of simple reactions, obtains various target products.The material molecule amount determines that structure is single, has very high decomposition temperature and relatively low sublimation temperature, can be applied in organic electroluminescent LED.
Description
Technical field
The present invention relates to the field of material technology of organic electroluminescence device technology, more particularly to a kind of organic hair of amboceptor
Light small molecule material and its preparation method and application.
Background technology
Organic electroluminescence device has obtained application in luminescence display field at present.Compared to polymer luminescent material
Speech, small molecule emitter material, which has, prepares simple, the advantages that molecular weight determines, structure is single, thus it is more potential push to it is wider
General commercial applications.At present, it is deposited based on small molecule material or solution is processed, prepare the technology of multilayer device just not
Disconnected ground development and progress, and obtain great progress.
In the past the research of organic electroluminescence device was had been achieved for significantly being in progress.Luminous organic material swashs electroluminescent
When hair, the singlet of generation and the theoretical proportions of triplet excitons are 1:3.The singlet energy level of common fluorescent material
Exciton transition, which returns ground state, to be allowed, and the exciton transition of triplet returns ground state and prohibits, therefore, exciton utilization rate
It is not high.But to singlet energy level and triplet can for the small material of difference, energy it is slightly lower and also last a long time three
Line state exciton can be transitted to by anti-intersystem crossing on singlet energy level by thermal excitation, then emits fluorescence, and this fluorescence claims
For thermal excitation delayed fluorescence.The exploitation of thermal excitation delayed fluorescence material has played pass to the efficiency for improving organic electroluminescence device
The effect of key, and can also have actively meaning for wider commercial applications to avoid the noble metal of phosphor material is used
Justice.
The organic electroluminescence device for the efficient stable being had use value, necessary not only for device architecture
Design is accurately regulated and controled, and very high requirement is also proposed to material therein particularly luminescent material.Therefore to shining
The corresponding property relationship of Molecular Design of material is explored, for prepare can show in the devices it is efficient, steady
It is fixed, low roll-off, the light emitting molecule mentality of designing of long-life provides guidance and is just particularly important.
Invention content
In order to overcome the disadvantages mentioned above of the prior art, the purpose of the present invention is to provide a kind of organic hairs of amboceptor with insufficient
Light small molecule material, while using two receptors of carbonyl sulfuryl as a kind of novel electron acceptors unit organic light emission small molecule,
The series material structure is single, and molecular weight determines, has preferable dissolubility and film forming.
Another object of the present invention is to provide the preparation method of above-mentioned amboceptor organic light emission small molecule material.
It is still another object of the present invention to provide the applications of above-mentioned amboceptor organic light emission small molecule material.
The purpose of the present invention is achieved through the following technical solutions：
A kind of amboceptor organic light emission small molecule material has any one of P1n, P2n, P3n, P4n chemical constitutions：
Wherein, Ar is arbitrary aromatic amine group in following (1)-(7)：
。
The amboceptor organic light emission small molecule material has any chemical constitution in P1-P28：
The preparation method of amboceptor organic light emission small molecule material, includes the following steps：
(1) any of the intermediate with (a)~(d) structures is prepared：
(2) under the protection of inert gas, intermediate, aromatic amine prepared by step (1) are added in organic solvent
Close object, alkali and catalyst are uniformly mixed, and are heated to reflux being stirred to react, via cooling down, extracting, being spin-dried for solvent, column chromatography, obtain
The organic molecule luminescent material based on novel amboceptor unit；
The intermediate is 1 with the molar ratio used in aromatic amine compounds:(2~2.5).
Preparation described in step (1) has any of the intermediate of (a)~(d) structures, specially：
Under nitrogen protection, raw material dibromo diphenyl sulfide is dissolved into anhydrous tetrahydro furan, is cooled to -70~-80 DEG C, according to
Secondary addition n-butyllithium solution and monobromo benzaldehyde, are stirred overnight after restoring to room temperature under N2 atmosphere, are added in after the completion of reaction
Ethyl alcohol terminates reaction；Reactant is through extracting, drying, filtering, isolated colourless liquid；
The dosage of the n-BuLi is 1~1.5 times of the mole of dibromo diphenyl sulfide；The monobromo benzaldehyde dosage is
1~1.5 times of the mole of dibromo diphenyl sulfide.
Step (2) is described to be heated to reflux being stirred to react, specially：
Temperature is 90~110 DEG C, the reaction time for 12~for 24 hours.
Step (2) described aromatic amine compounds are appointing in carbazole, 9,9 '-dimethyl acridinium, phenoxazines or phenthazine
Meaning is a kind of.
Step (2) described alkali is organic base, and dosage is 1.8~2.5 times of molar equivalents of aromatic amine compounds.
Step (2) catalyst is made of palladium and three tertiary butyl phosphines.
The step (2) organic solvent is toluene.
Application of the amboceptor organic light emission small molecule material in electroluminescent diode.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) amboceptor organic light emission small molecule material of the invention, while using two receptors of carbonyl sulfuryl as a kind of
Novel electron acceptors unit, the molecule for obtaining D-A structure is connect with common electron donor unit has that structure is single, molecular weight
It determines, multi-stage synthesis high repeatability and other advantages.
(2) amboceptor organic light emission small molecule material of the invention, it is stronger containing having there are two the material of receptor structure
Intramolecular electron transfer, can smaller single triplet easy to implement it is poor, while ensure higher fluorescence quantum yield.Cause
This, while obtaining thermal activation delayed fluorescence property, can realize very high external quantum efficiency and the rolling of very low efficiency in the devices
Drop.
(3) amboceptor organic light emission small molecule material of the invention, can be by changing the type of linking group, so as to adjust
Save the photoelectric devices performances such as the photochromic of material, charge transport properties.
(4) structure of the invention can play the conjugation of controlled material by adjusting the position and quantity that group connects
Length, Cloud Distribution, carrier transmission characteristics and film forming.
(5) amboceptor organic light emission small molecule material of the invention can realize that Intramolecular electron transfer acts on, and it is double
Pole transmission characteristic reduces the unbalanced problem of unipolarity luminescent material carrier, so as to simplify device architecture, improves device
Part performance.
(6) amboceptor organic light emission small molecule material of the invention has very high decomposition temperature and relatively low distillation temperature
Degree, is easily sublimed into the luminescent material of high-purity, can be applied to vapor deposition type electroluminous organic small molecular diode.
(7) it is of the invention to prepare simple, by a series of simple reactions, obtain various target products.
Description of the drawings
Fig. 1 is the Absorption and emission spectra of P18, P20 in toluene solution.
Fig. 2 is Current density-voltage-brightness curve of the organic light emitting diode device comprising P18, P20.
Fig. 3 is the luminance-current efficiency of the organic light emitting diode device comprising P18, P20 and brightness-power efficiency song
Line.
Fig. 4 is the alternating temperature transient lifetime spectrogram of P18, P20 in the film.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The present embodiment prepares intermediate 1 to 14 and compound P1：
The preparation process of intermediate 1 is：
In a nitrogen atmosphere, it is successively added in 250ml three-necked flasks to bromo-iodobenzene 11.7g (40.0mmol), nine water sulphur
Change sodium 5.8g (24.0mmol), cuprous iodide (CuI) 336mg (0.1equ), Anhydrous potassium carbonate 5.4g (40.0mmol), N, N- bis-
Methylformamide (DMF) 80mL.120 DEG C are heated to, is protected from light and is stirred to react 18 hours.It after reaction, will be in reaction system
Solvent hang it is dry, with dichloromethane and water extraction three times, take organic phase.Dichloromethane is removed in vacuum distillation, and silicagel column purification obtains
The intermediate 7g of structural formula 1, yield 94%, C12H8Br2S M/Z=341.87.m/z:343.87 (100.0%), 341.87
(51.4%), 345.87 (48.6%), 344.87 (9.7%), 346.87 (6.3%), 345.87 (4.5%), 342.87
(4.4%), 344.87 (3.2%), 343.87 (2.3%), 342.87 (2.2%), 347.86 (2.2%)；Elemental analysis：C,
41.89；H,2.34；Br,46.45；S,9.32.
2 specific implementation step of intermediate is：
In a nitrogen atmosphere, bromo-iodobenzene 11.7g (40.0mmol) between successively being added in 250ml three-necked flasks, nine water sulphur
Change sodium 5.8g (24.0mmol), cuprous iodide (CuI) 336mg (0.1equ), Anhydrous potassium carbonate 5.4g (40.0mmol), N, N- bis-
Methylformamide (DMF) 80mL.120 DEG C are heated to, is protected from light and is stirred to react 18 hours.It after reaction, will be in reaction system
Solvent hang it is dry, with dichloromethane and water extraction three times, take organic phase.Dichloromethane is removed in vacuum distillation, and silicagel column purification obtains
The intermediate 6.3g of structural formula 1, yield 85%, C12H8Br2S M/Z=341.87.m/s：m/z:(100.0%), 343.87
341.87 (51.4%), 345.87 (48.6%), 344.87 (9.7%), 346.87 (6.3%), 345.87 (4.5%),
342.87 (4.4%), 344.87 (3.2%), 343.87 (2.3%), 342.87 (2.2%), 347.86 (2.2%)；Element point
Analysis：C,41.89；H,2.34；Br,46.45；S,9.32.
The preparation process of intermediate 3 is：
In a nitrogen atmosphere, 5.1g (15mmol) compound 1 is added in dry 250ml three-necked flasks, is squeezed into later
It is new to steam tetrahydrofuran 50mL.2.5M n-BuLis (nBuLi) 6mL is squeezed into after reactor is cooled to -78 DEG C dropwise, keeps low temperature
Stirring is slowly squeezed into after two hours steams tetrahydrofuran solution 50mL dissolved with the new of 2.7g (15mmol) p-bromobenzaldehyde, continues to keep the temperature
Stirring one and a half hours.Reaction is carried to room temperature later, is stirred overnight.After reaction, the solvent in reaction system is hanged it is dry,
With dichloromethane and water extraction three times, organic phase is taken.Dichloromethane is removed in vacuum distillation, and silicagel column purification obtains structural formula 3
Intermediate 4.2g, yield 62%, C19H14Br2OS M/Z=450.19.m/z:449.91 (100.0%), 447.91
(51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92
(6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92
(1.2%)；Elemental analysis：C,50.69；H,3.13；Br,35.50；O,3.55；S,7.12.
The preparation process of intermediate 4 is：
In a nitrogen atmosphere, 5.1g (15mmol) compound 2 is added in dry 250ml three-necked flasks, is squeezed into later
It is new to steam tetrahydrofuran 50mL.2.5M n-BuLis (nBuLi) 6mL is squeezed into after reactor is cooled to -78 DEG C dropwise, keeps low temperature
Stirring is slowly squeezed into after two hours steams tetrahydrofuran solution 50mL dissolved with the new of 2.7g (15mmol) p-bromobenzaldehyde, continues to keep the temperature
Stirring one and a half hours.Reaction is carried to room temperature later, is stirred overnight.After reaction, the solvent in reaction system is hanged it is dry,
With dichloromethane and water extraction three times, organic phase is taken.Dichloromethane is removed in vacuum distillation, and silicagel column purification obtains structural formula 4
Intermediate 4.5g, yield 67%, C19H14Br2OS M/Z=450.19.m/z:449.91 (100.0%), 447.91
(51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92
(6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92
(1.2%)；Elemental analysis：C,50.69；H,3.13；Br,35.50；O,3.55；S,7.12.
The preparation process of intermediate 5 is：
In a nitrogen atmosphere, 5.1g (15mmol) compound 1 is added in dry 250ml three-necked flasks, is squeezed into later
It is new to steam tetrahydrofuran 50mL.2.5M n-BuLis (nBuLi) 6mL is squeezed into after reactor is cooled to -78 DEG C dropwise, keeps low temperature
Stirring is slowly squeezed into after two hours steams tetrahydrofuran solution 50mL dissolved with the new of 2.7g (15mmol) 3-bromobenzaldehyde, continues to keep the temperature
Stirring one and a half hours.Reaction is carried to room temperature later, is stirred overnight.After reaction, the solvent in reaction system is hanged it is dry,
With dichloromethane and water extraction three times, organic phase is taken.Dichloromethane is removed in vacuum distillation, and silicagel column purification obtains structural formula 5
Intermediate 4g, yield 60%, C19H14Br2OS M/Z=450.19.m/z:449.91 (100.0%), 447.91 (51.4%),
451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%),
451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%)；Element point
Analysis：C,50.69；H,3.13；Br,35.50；O,3.55；S,7.12.
The specific implementation step of intermediate 6 is：
In a nitrogen atmosphere, 5.1g (15mmol) compound 2 is added in dry 250ml three-necked flasks, is squeezed into later
It is new to steam tetrahydrofuran 50mL.2.5M n-BuLis (nBuLi) 6mL is squeezed into after reactor is cooled to -78 DEG C dropwise, keeps low temperature
Stirring is slowly squeezed into after two hours steams tetrahydrofuran solution 50mL dissolved with the new of 2.7g (15mmol) 3-bromobenzaldehyde, continues to keep the temperature
Stirring one and a half hours.Reaction is carried to room temperature later, is stirred overnight.After reaction, the solvent in reaction system is hanged it is dry,
With dichloromethane and water extraction three times, organic phase is taken.Dichloromethane is removed in vacuum distillation, and silicagel column purification obtains structural formula 6
Intermediate 4g, yield 60%, C19H14Br2OS M/Z=450.19.m/z:449.91 (100.0%), 447.91 (51.4%),
451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%),
451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%)；Element point
Analysis：C,50.69；H,3.13；Br,35.50；O,3.55；S,7.12.
7 specific preparation process of intermediate is：
3.4g (7.6mmol) compound 3 is successively added in 250ml single-necked flasks, adding in the stirring of 100mL dichloromethane will
It is dissolved, and is added in 4.92g (22.8mmol) pyridine chlorochromate (PCC) later, is stirred at room temperature 8 hours.After reaction, will
Solvent in reaction system hang it is dry, with dichloromethane and water extraction three times, take organic phase.Dichloromethane, silicon are removed in vacuum distillation
Rubber column gel column purifies, and obtains the intermediate 3.2g of structural formula 9, yield 94%, C19H12Br2OS M/Z=448.17.m/z:447.90
(100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90
(9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89
(2.2%), 449.90 (1.2%)；Elemental analysis：C,50.92；H,2.70；Br,35.66；O,3.57；S,7.15.
The preparation process of intermediate 8 is：
1g (2.4mmol) compound 7 is added in 250ml single-necked flasks, add in 80ml dichloromethane and is stirred its is molten
Solution, adds 2ml hydrogen peroxide later plus per half an hour, and reaction continues 6 hours.After reaction, by the solvent in reaction system
It is outstanding dry, it is extracted three times with dichloromethane and water, takes organic phase.Dichloromethane is removed in vacuum distillation, and silicagel column purification obtains structure
The intermediate 0.9g of formula 1, yield 80%, C19H12Br2O3S M/Z=480.17.m/z:479.89 (100.0%), 477.89
(51.4%), 481.88 (48.6%), 480.89 (10.8%), 478.89 (10.6%), 482.89 (10.0%), 480.89
(9.7%), 481.88 (4.5%), 479.88 (2.3%), 483.88 (2.2%), 481.89 (1.5%)；Elemental analysis：C,
47.53；H,2.52；Br,33.28；O,10.00；S,6.68.
The preparation process of intermediate 9 is：
Change the compound 3 in the reaction step for preparing intermediate 7 into compound 4, remaining step obtains as raw material
The intermediate 3.1g of structural formula 9, yield 91%, C19H12Br2OS M/Z=448.17.m/z:(100.0%), 447.90
445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%),
446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90
(1.2%)；Elemental analysis：C,50.92；H,2.70；Br,35.66；O,3.57；S,7.15.
The tool preparation process of intermediate 10 is：
Change the compound 7 in the reaction step for preparing intermediate 8 into compound 9, remaining step obtains as raw material
The intermediate 0.95g of structural formula 10, yield 82%, C19H12Br2O3S M/Z=480.17.C19H12Br2O3S M/Z=
480.17.m/z:479.89 (100.0%), 477.89 (51.4%), 481.88 (48.6%), 480.89 (10.8%),
478.89 (10.6%), 482.89 (10.0%), 480.89 (9.7%), 481.88 (4.5%), 479.88 (2.3%),
483.88 (2.2%), 481.89 (1.5%)；Elemental analysis：C,47.53；H,2.52；Br,33.28；O,10.00；S,6.68.
The preparation process of intermediate 11 is：
Change the compound 3 in the reaction step for preparing intermediate 7 into compound 5, remaining step obtains as raw material
The intermediate 3g of structural formula 11, yield 87%, C19H12Br2OS M/Z=448.17.m/z:(100.0%), 447.90
445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%),
446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90
(1.2%)；Elemental analysis：C,50.92；H,2.70；Br,35.66；O,3.57；S,7.15.The preparation process of intermediate 12 is：
Change the compound 7 for the reaction step for preparing intermediate 8 into compound 11, remaining step obtains as raw material
The intermediate 0.9g of structural formula 12, yield 78%, C19H12Br2O3S M/Z=480.17.C19H12Br2O3S M/Z=
480.17.m/z:479.89 (100.0%), 477.89 (51.4%), 481.88 (48.6%), 480.89 (10.8%),
478.89 (10.6%), 482.89 (10.0%), 480.89 (9.7%), 481.88 (4.5%), 479.88 (2.3%),
483.88 (2.2%), 481.89 (1.5%)；Elemental analysis：C,47.53；H,2.52；Br,33.28；O,10.00；S,6.68.
The preparation process of intermediate 13 is：
Change the compound 3 for the reaction step for preparing intermediate 7 into compound 6, remaining step is tied as raw material
The intermediate 3g of structure formula 13, yield 87%, C19H12Br2OS M/Z=448.17.m/z:447.90 (100.0%), 445.90
(51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90
(6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90
(1.2%)；Elemental analysis：C,50.92；H,2.70；Br,35.66；O,3.57；S,7.15.
Intermediate 14 is for preparation process：
Change the compound 7 in the reaction step for preparing intermediate 8 into compound 13, remaining step obtains as raw material
To the intermediate 0.92g of structural formula 14, yield 80%, C19H12Br2O3S M/Z=480.17.C19H12Br2O3S M/Z=
480.17.m/z:479.89 (100.0%), 477.89 (51.4%), 481.88 (48.6%), 480.89 (10.8%),
478.89 (10.6%), 482.89 (10.0%), 480.89 (9.7%), 481.88 (4.5%), 479.88 (2.3%),
483.88 (2.2%), 481.89 (1.5%)；Elemental analysis：C,47.53；H,2.52；Br,33.28；O,10.00；S,6.68.：
The preparation process of compound P1 is：
Under nitrogen protection, the addition 100ml toluene into three-necked flask, 1g intermediates 14 (2.99mmol), the two of 1.26g
Aniline (2.5equ) adds in 0.90g tertiary butyl sodium alkoxide, adds 59.8mg palladiums under stiring, three tertiary butyl phosphines, at 90 DEG C
Reaction is overnight.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 1.30g, yield 85%.Molecular formula：
C43H32N2O3S；M/Z=656.80 theoretical values:m/z:656.21 (100.0%), 657.22 (46.5%), 658.22
(10.6%), 658.21 (4.5%), 659.21 (2.1%)；Elemental analysis:C,78.63；H,4.91；N,4.27；O,7.31；S,
4.88。
Embodiment 2
The present embodiment prepare compound P2, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 1 is substituted for the intermediate 10 of equivalent, other raw materials and step are same as embodiment
1, obtain the product 1.50g of structural formula P2, yield 76%.Molecular formula：C43H32N2O3S；M/Z=656.80 theoretical values:m/z:
656.21 (100.0%), 657.22 (46.5%), 658.22 (10.6%), 658.21 (4.5%), 659.21 (2.1%)；Member
Element analysis:C,78.63；H,4.91；N,4.27；O,7.31；S,4.88.
Embodiment 3
The present embodiment prepare compound P3, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 1 in the preparation process of P1 is substituted for the intermediate 12 of equivalent, other raw materials and step
Suddenly embodiment 1 is same as, obtains the product 1.45g of structural formula P3, yield 74%.Molecular formula：C43H32N2O3S；M/Z=656.80
Theoretical value:m/z:656.21 (100.0%), 657.22 (46.5%), 658.22 (10.6%), 658.21 (4.5%), 659.21
(2.1%)；Elemental analysis:C,78.63；H,4.91；N,4.27；O,7.31；S,4.88.
Embodiment 4
The present embodiment prepare compound P4, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 1 in the preparation process of P1 is substituted for the intermediate 8 of equivalent, other raw materials and step
Embodiment 15 is same as, obtains the product 1.45g of structural formula P4, yield 74%.Molecular formula：C43H32N2O3S；M/Z=656.80
Theoretical value:m/z:656.21 (100.0%), 657.22 (46.5%), 658.22 (10.6%), 658.21 (4.5%), 659.21
(2.1%)；Elemental analysis:C,78.63；H,4.91；N,4.27；O,7.31；S,4.88.
Embodiment 5
The present embodiment prepare compound P5, structural formula and synthetic route are as follows：
Specific implementation step is：
Under nitrogen protection, 100ml toluene, 1g intermediates 14 (2.99mmol), the click of 1.26g are added in into three-necked flask
Azoles (2.5equ) adds in 0.90g tertiary butyl sodium alkoxide, adds 59.8mg palladiums under stiring, three tertiary butyl phosphines, anti-at 90 DEG C
It should stay overnight.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 0.85g, yield 56%.Molecular formula：
C43H28N2O3S；M/Z=652.77 theoretical values:m/z:652.18 (100.0%), 653.19 (46.5%), 654.19
(10.6%), 654.18 (4.5%), 655.18 (2.1%)；Elemental analysis:C,79.12；H,4.32；N,4.29；O,7.35；S,
4.91。
Embodiment 6
The present embodiment prepare compound P6, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 5 is substituted for the intermediate 10 of equivalent, other raw materials and step are same as embodiment
5, obtain the product 0.80g of structural formula P6, yield 50%.Molecular formula：C43H28N2O3S；M/Z=652.77 theoretical values:m/z:
652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%)；Member
Element analysis:C,79.12；H,4.32；N,4.29；O,7.35；S,4.91.
Embodiment 7
The present embodiment prepare compound P7, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 5 is substituted for the intermediate 12 of equivalent, other raw materials and step are same as embodiment
5, obtain the product 0.80g of structural formula P7, yield 50%.Molecular formula：C43H28N2O3S；M/Z=652.77 theoretical values:m/z:
652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%)；Member
Element analysis:C,79.12；H,4.32；N,4.29；O,7.35；S,4.91.
Embodiment 8
The present embodiment prepare compound P8, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 5 is substituted for the intermediate 8 of equivalent, other raw materials and step are same as embodiment 5,
Obtain the product 0.95g of structural formula P8, yield 62%.Molecular formula：C43H28N2O3S；M/Z=652.77 theoretical values:m/z:
652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%)；Member
Element analysis:C,79.12；H,4.32；N,4.29；O,7.35；S,4.91.
Embodiment 9
The present embodiment prepare compound P9, structural formula and synthetic route are as follows：
Specific implementation step is：
Under nitrogen protection, 100ml toluene, 1g intermediates 14 (2.99mmol), the fen of 1.50g are added in into three-necked flask
Thiazine (2.5equ) adds in 0.90g tertiary butyl sodium alkoxide, adds 59.8mg palladiums under stiring, three tertiary butyl phosphines, at 90 DEG C
Reaction is overnight.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 1.21g, yield 63%.Molecular formula：
C43H28N2O3S3；M/Z=716.13 theoretical values:m/z:716.13 (100.0%), 717.13 (46.5%), 718.12
(13.6%), 718.13 (10.6%), 719.13 (6.3%), 717.13 (2.4%), 720.13 (1.4%), 718.13
(1.1%)；Elemental analysis:C,72.04；H,3.94；N,3.91；O,6.70；S,13.42.
Embodiment 10
The present embodiment prepare compound P10, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 9 is substituted for the intermediate 10 of equivalent, other raw materials and step are same as embodiment
9, obtain the product 1.02g of structural formula P10, yield 55%.Molecular formula：C43H28N2O3S3；M/Z=716.13 theoretical values:m/z:
716.13 (100.0%), 717.13 (46.5%), 718.12 (13.6%), 718.13 (10.6%), 719.13 (6.3%),
717.13 (2.4%), 720.13 (1.4%), 718.13 (1.1%)；Elemental analysis:C,72.04；H,3.94；N,3.91；O,
6.70；S,13.42.
Embodiment 11
The present embodiment prepare compound P11, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 9 is substituted for the intermediate 12 of equivalent, other raw materials and step are same as embodiment
9, obtain the product 0.95g of structural formula P11, yield 50%.Molecular formula：C43H28N2O3S3；M/Z=716.13 theoretical values:m/z:
716.13 (100.0%), 717.13 (46.5%), 718.12 (13.6%), 718.13 (10.6%), 719.13 (6.3%),
717.13 (2.4%), 720.13 (1.4%), 718.13 (1.1%)；Elemental analysis:C,72.04；H,3.94；N,3.91；O,
6.70；S,13.42.
Embodiment 12
The present embodiment prepare compound P12, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 9 is substituted for the intermediate 8 of equivalent, other raw materials and step are same as embodiment 9,
Obtain the product 1.21g of structural formula P12, yield 61%.Molecular formula：C43H28N2O3S3；M/Z=716.13 theoretical values:m/z:
716.13 (100.0%), 717.13 (46.5%), 718.12 (13.6%), 718.13 (10.6%), 719.13 (6.3%),
717.13 (2.4%), 720.13 (1.4%), 718.13 (1.1%)；Elemental analysis:C,72.04；H,3.94；N,3.91；O,
6.70；S,13.42.
Embodiment 13
The present embodiment prepare compound P13, structural formula and synthetic route are as follows：
Specific implementation step is：
Under nitrogen protection, 100ml toluene, 1g intermediates 14 (2.99mmol), the fen of 1.40g are added in into three-necked flask
Oxazine (2.5equ) adds in 0.90g tertiary butyl sodium alkoxide, adds 59.8mg palladiums under stiring, three tertiary butyl phosphines, at 90 DEG C
Reaction is overnight.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 1.15g, yield 62%.Molecular formula：
C43H28N2O5S；M/Z=684.17 theoretical values:m/z:684.17 (100.0%), 685.18 (46.5%), 686.18
(10.6%), 686.17 (4.5%), 687.17 (2.1%), 686.18 (1.0%)；Elemental analysis:C,75.42；H,4.12；N,
4.09；O,11.68；S,4.68.
Embodiment 14
The present embodiment prepare compound P14, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 13 is substituted for the intermediate 10 of equivalent, other raw materials and step are same as embodiment
13, obtain the product 1.02g of structural formula P14, yield 55%.Molecular formula：C43H28N2O5S；M/Z=684.17 theoretical values:m/z:
684.17 (100.0%), 685.18 (46.5%), 686.18 (10.6%), 686.17 (4.5%), 687.17 (2.1%),
686.18 (1.0%)；Elemental analysis:C,75.42；H,4.12；N,4.09；O,11.68；S,4.68.
Embodiment 15
The present embodiment prepare compound P15, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 13 is substituted for the intermediate 12 of equivalent, other raw materials and step are same as embodiment
13, obtain the product 0.95g of structural formula P15, yield 50%.Molecular formula：C43H28N2O5S；M/Z=684.17 theoretical values:m/z:
684.17 (100.0%), 685.18 (46.5%), 686.18 (10.6%), 686.17 (4.5%), 687.17 (2.1%),
686.18 (1.0%)；Elemental analysis:C,75.42；H,4.12；N,4.09；O,11.68；S,4.68.
Embodiment 16
The present embodiment prepare compound P16, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 13 is substituted for the intermediate 8 of equivalent, other raw materials and step are same as embodiment
13, obtain the product 1.21g of structural formula P16, yield 61%.Molecular formula：C43H28N2O5S；M/Z=684.17 theoretical values:m/z:
684.17 (100.0%), 685.18 (46.5%), 686.18 (10.6%), 686.17 (4.5%), 687.17 (2.1%),
686.18 (1.0%)；Elemental analysis:C,75.42；H,4.12；N,4.09；O,11.68；S,4.68.
Embodiment 17
The present embodiment prepare compound P17, structural formula and synthetic route are as follows：
Specific implementation step is：
Under nitrogen protection, the addition 100ml toluene into three-necked flask, 1g intermediates 14 (2.99mmol), the two of 1.40g
Methylacridine (2.5equ) adds in 0.90g tertiary butyl sodium alkoxide, adds 59.8mg palladiums under stiring, three tertiary butyl phosphines, and 90
It is reacted overnight at DEG C.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 1.50g, yield 68%.Molecular formula：
C49H40N2O3S；M/Z=736.28 theoretical values:736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%),
738.27 (4.5%), 739.28 (2.4%), 739.29 (1.5%)；Elemental analysis:C,79.86；H,5.47；N,3.80；O,
6.51；S,4.35.
Embodiment 18
The present embodiment prepare compound P18, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 17 is substituted for the intermediate 10 of equivalent, other raw materials and step are same as embodiment
17, obtain the product 1.22g of structural formula P18, yield 55%.Molecular formula：C49H40N2O3S；M/Z=736.28 theoretical values:
736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%), 738.27 (4.5%), 739.28 (2.4%),
739.29 (1.5%)；Elemental analysis:C,79.86；H,5.47；N,3.80；O,6.51；S,4.35.
Absorption and emission spectras of the compound P18 manufactured in the present embodiment in toluene solution is as shown in Figure 1, can by figure
Know, which there are weak CT absorption peaks, belongs to CT class molecules, meets thermal activation delayed fluorescence molecular characterization, the transmitting of the molecule
Peak belongs to green emission in 540nm.
Embodiment 19
The present embodiment prepare compound P19, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 17 is substituted for the intermediate 12 of equivalent, other raw materials and step are same as embodiment
17, obtain the product 1.18g of structural formula P19, yield 50%.Molecular formula：C49H40N2O3S；M/Z=736.28 theoretical values:
736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%), 738.27 (4.5%), 739.28 (2.4%),
739.29 (1.5%)；Elemental analysis:C,79.86；H,5.47；N,3.80；O,6.51；S,4.35.
Embodiment 20
The present embodiment prepare compound P20, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 17 is substituted for the intermediate 8 of equivalent, other raw materials and step are same as
Embodiment 17 obtains the product 1.38g of structural formula P20, yield 61%.Molecular formula：C49H40N2O3S；M/Z=
736.28 theoretical value:736.28 (100.0%), 737.28 (53.0%), 738.28 (13.8%), 738.27 (4.5%),
739.28 (2.4%), 739.29 (1.5%)；Elemental analysis:C,79.86；H,5.47；N,3.80；O,6.51；S,4.35.
Absorption and emission spectras of the compound P20 manufactured in the present embodiment in toluene solution is as shown in Figure 1, as seen from the figure
The molecule has weak CT absorption peaks, belongs to CT class molecules, meets thermal activation delayed fluorescence molecular characterization, and the emission peak of the molecule exists
550nm belongs to yellowish green light emitting.The molecule is acted on due to changing the electric charge transfer of intramolecular, emission peak red shift.
Embodiment 21
The present embodiment prepare compound P21, structural formula and synthetic route are as follows：
Specific implementation step is：
Under nitrogen protection, the addition 100ml toluene into three-necked flask, 1g intermediates 14 (2.99mmol), the 3 of 1.26g,
6 tert-butyl carbazoles (2.5equ) add in 0.90g tertiary butyl sodium alkoxide, add 59.8mg palladiums, three tertiary butyls under stiring
Phosphine is reacted overnight at 90 DEG C.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 0.85g, yield 56%.Point
Minor：C59H60N2O3S；M/Z=876.43 theoretical values:m/z:876.43 (100.0%), 877.44 (63.8%), 878.44
(20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%)；Elemental analysis:C,80.79；H,6.89；N,
3.19；O,5.47；S,3.65.
Embodiment 22
The present embodiment prepare compound P22, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 21 is substituted for the intermediate 10 of equivalent, other raw materials and step are same as embodiment
21, obtain the product 0.80g of structural formula P22, yield 50%.Molecular formula：C59H60N2O3S；M/Z=876.43 theoretical values:m/z:
876.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%),
879.43 (2.9%)；Elemental analysis:C,80.79；H,6.89；N,3.19；O,5.47；S,3.65.
Embodiment 23
The present embodiment prepare compound P23, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 21 is substituted for the intermediate 12 of equivalent, other raw materials and step are same as embodiment
21, obtain the product 0.80g of structural formula P23, yield 50%.Molecular formula：C59H60N2O3S；M/Z=876.43 theoretical values:m/z:
876.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%),
879.43 (2.9%)；Elemental analysis:C,80.79；H,6.89；N,3.19；O,5.47；S,3.65.
Embodiment 24
The present embodiment prepare compound P24, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 21 is substituted for the intermediate 8 of equivalent, other raw materials and step are same as
Embodiment 21 obtains the product 0.95g of structural formula P24, yield 62%.Molecular formula：C59H60N2O3S；M/Z=
876.43 theoretical value:m/z:876.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%),
879.44 (3.3%), 879.43 (2.9%)；Elemental analysis:C,80.79；H,6.89；N,3.19；O,5.47；S,3.65.
Embodiment 25
The present embodiment prepare compound P25, structural formula and synthetic route are as follows：
Specific implementation step is：
Under nitrogen protection, the addition 100ml toluene into three-necked flask, 1g intermediates 14 (2.99mmol), the 3 of 1.40g,
6 fert-butyidimethylsilyl acridines (2.5equ) add in 0.90g tertiary butyl sodium alkoxide under stiring, add 59.8mg palladiums, and three is special
Butyl phosphine is reacted overnight at 90 DEG C.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 1.50g, yield
68%.Molecular formula：C65H72N2O3S；M/Z=960.53 theoretical values:960.53 (100.0%), 961.53 (70.3%),
962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%), 963.53 (3.2%), 964.53 (1.1%)；Element point
Analysis:C,81.21；H,7.55；N,2.91；O,4.99；S,3.33.
Embodiment 26
The present embodiment prepare compound P26, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 25 is substituted for the intermediate 10 of equivalent, other raw materials and step are same as embodiment
25, obtain the product 1.22g of structural formula P26, yield 55%.Molecular formula：C65H72N2O3S；M/Z=960.53 theoretical values:
960.53 (100.0%), 961.53 (70.3%), 962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%),
963.53 (3.2%), 964.53 (1.1%)；Elemental analysis:C,81.21；H,7.55；N,2.91；O,4.99；S,3.33.
Embodiment 27
The present embodiment prepare compound P27, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 25 is substituted for the intermediate 12 of equivalent, other raw materials and step are same as embodiment
25, obtain the product 1.18g of structural formula P27, yield 50%.Molecular formula：C65H72N2O3S；M/Z=960.53 theoretical values:
960.53 (100.0%), 961.53 (70.3%), 962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%),
963.53 (3.2%), 964.53 (1.1%)；Elemental analysis:C,81.21；H,7.55；N,2.91；O,4.99；S,3.33.
Embodiment 28
The present embodiment prepare compound P28, structural formula and synthetic route are as follows：
Specific implementation step is：
Intermediate 14 in embodiment 25 is substituted for the intermediate 8 of equivalent, other raw materials and step are same as embodiment
25, obtain the product 1.38g of structural formula P28, yield 61%.Molecular formula：C65H72N2O3S；M/Z=960.53 theoretical values:
960.53 (100.0%), 961.53 (70.3%), 962.53 (24.3%), 963.54 (4.7%), 962.52 (4.5%),
963.53 (3.2%), 964.53 (1.1%)；Elemental analysis:C,81.21；H,7.55；N,2.91；O,4.99；S,3.33.
Embodiment 29
The present embodiment prepares double carbonyl control compounds P29, and structural formula and synthetic route are as follows：
Specific implementation step is：
Under nitrogen protection, 100ml toluene, the bis- carbonyl intermediates of 1g (2.99mmol), 1.26g are added in into three-necked flask
3,6 tert-butyl carbazoles (2.5equ), add in 0.90g tertiary butyl sodium alkoxide under stiring, add 59.8mg palladiums, three special fourths
Base phosphine is reacted overnight at 90 DEG C.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 0.90g, yield 65%.
Molecular formula：C44H32N2O2；M/Z=620.25 theoretical values:m/z:620.25 (100.0%), 621.25 (47.6%), 622.25
(11.1%)；Elemental analysis:C,85.14；H,5.20；N,4.51；O,5.15.
Embodiment 30
The present embodiment prepares bis sulfone base control compounds P30, and structural formula and synthetic route are as follows：
Under nitrogen protection, 100ml toluene, 1g bis sulfone base intermediates (2.99mmol), 1.26g are added in into three-necked flask
3,6 tert-butyl carbazoles (2.5equ), add in 0.90g tertiary butyl sodium alkoxide under stiring, add 59.8mg palladiums, three special fourths
Base phosphine is reacted overnight at 90 DEG C.Cooling extracts organic phase with dichloromethane, is spin-dried for, crosses column.Obtain product 0.89g, yield 64%.
Molecular formula：C42H32N2O4S2；M/Z=692.18 theoretical values:m/z:692.18 (100.0%), 693.18 (45.4%),
694.19 (10.1%), 694.18 (9.0%), 695.18 (4.1%), 693.18 (1.6%)；Elemental analysis:C,72.81；H,
4.66；N,4.04；O,9.24；S,9.25.
Here is Application Example of the compounds of this invention in Organic Light Emitting Diode (OLED) device：
Embodiment 30-39
Using luminescent material of the compound of the present invention as OLED device, the general-purpose device structure of implementation is as follows：
ITO (95nm)/TAPC (20nm)/Pn (10wt%):CBP(35nm)/TmPyPB(55nm)/LiF(1nm)/Al
(100nm)
Wherein ITO is anode, and TAPC is hole injection layer, and CBP is that luminescent material doped body TmPyPB is electron-transport
Layer, LiF is electron injecting layer, and Al is cathode.
Material therefor structural formula is as follows：
Device fabrication process is as follows：Transparent electro-conductive glass is ultrasonically treated in cleaning agent, then clear with deionized water
It washes, in acetone：The in the mixed solvent ultrasound oil removing of ethyl alcohol is baked to removes moisture completely under a clean environment, uses ultraviolet light
And ozone clean, and with low energy electric ion bombardment.
The above-mentioned glass with anode ITO is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, in above-mentioned sun
On the film of pole withDeposition rate vapor deposition organic material layer, wherein vapor deposition luminescent layer, CBP and luminescent material are put respectively
It puts in two evaporation sources, the mixed proportion of the two is controlled by certain deposition rate.Later again withDeposition
LiF is deposited in rate, withDeposition rate evaporating Al electrode, obtain the organic light emitting diode device of the present embodiment.
The Current density-voltage of the organic light emitting diode device of the present embodiment-brightness curve figure, maximum extrinsic current effect
As shown in figures 2-3, basic characterize data is as shown in table 1 for rate-brightness, maximum external power ciency-luminance graph of relation.
P18, P20 of the present embodiment alternating temperature transient lifetime spectrum in the film as shown in figure 4, with the raising of temperature,
Long-life ingredient in transient state spectrum increases, illustrate the long-life ingredient of molecule and have the property of thermal activation, it was demonstrated that this kind of point
Son is the molecule with thermal activation delayed fluorescence characteristic.
The test result for the OLED device that table 1 is made
Explanation：This kind of amboceptor material can obtain very high current efficiency and outer quantum effect in simple device architecture
Rate.As can be seen from the above table, compared to the material of traditional single receptor, even if having switched many donors of different strengths and weaknesses, two
The combination of a receptor unit makes it easier to realize small single triplet difference so as to which material be made to obtain thermal activation delayed fluorescence
Property, so as to break spin statistics rule, realize more than 5% external quantum efficiency, and at the same time can realize from blue green light to
The photochromic variation of yellow light.Meanwhile the preferable bipolar transmission performance of light emitting molecule cause device open bright voltage all in 3-4 volts
Between, it is relatively low to open bright voltage and ensure the higher power efficiency of electroluminescent device.This is but also this kind of light emitting molecule exists
Possess bigger application space compared to known materials in OLED device.
Compare amboceptor the molecule P29 and P30 containing double carbonyls or bis sulfone base of similar structure, not isoacceptor composition it is double by
Body molecule P4 has shown considerably higher maximum external quantum efficiency and current efficiency and lower under identity unit structure
Bright voltage is opened, device performance has significant raising, has highlighted this kind of amboceptor organic light emission small molecule material in molecule
Advance in design.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of amboceptor organic light emission small molecule material, which is characterized in that there is any one of P1n, P2n, P3n, P4n changes
Learn structure：
Wherein, Ar is arbitrary aromatic amine group in following (1)-(7)：
2. amboceptor organic light emission small molecule material according to claim 1, which is characterized in that have any in P1-P28
Kind chemical constitution：
3. the preparation method of amboceptor organic light emission small molecule material, which is characterized in that include the following steps：
(1) any of the intermediate with (a)~(d) structures is prepared：
(2) under the protection of inert gas, in organic solvent add in step (1) prepare intermediate, aromatic amine compounds,
Alkali and catalyst are uniformly mixed, and are heated to reflux being stirred to react, and via cooling down, extracting, being spin-dried for solvent, column chromatography, are obtained described
Organic molecule luminescent material based on novel amboceptor unit；
The intermediate is 1 with the molar ratio used in aromatic amine compounds:(2~2.5).
4. the preparation method of amboceptor organic light emission small molecule material according to claim 3, which is characterized in that step
(1) preparation described in has any of the intermediate of (a)~(d) structures, specially：
Under nitrogen protection, raw material dibromo diphenyl sulfide is dissolved into anhydrous tetrahydro furan, is cooled to -70~-80 DEG C, added successively
Enter n-butyllithium solution and monobromo benzaldehyde, be stirred overnight under N2 atmosphere after restoring to room temperature, ethyl alcohol is added in after the completion of reaction
Terminate reaction；Reactant is through extracting, drying, filtering, isolated colourless liquid；
The dosage of the n-BuLi is 1~1.5 times of the mole of dibromo diphenyl sulfide；The monobromo benzaldehyde dosage is dibromo
1~1.5 times of the mole of diphenyl sulfide.
5. the preparation method of amboceptor organic light emission small molecule material according to claim 3, which is characterized in that step
(2) it is described to be heated to reflux being stirred to react, specially：
Temperature is 90~110 DEG C, the reaction time for 12~for 24 hours.
6. the preparation method of amboceptor organic light emission small molecule material according to claim 3, which is characterized in that step
(2) aromatic amine compounds are any one in carbazole, 9,9 '-dimethyl acridinium, phenoxazines or phenthazine.
7. the preparation method of amboceptor organic light emission small molecule material according to claim 3, which is characterized in that step
(2) alkali is organic base, and dosage is 1.8~2.5 times of molar equivalents of aromatic amine compounds.
8. the preparation method of amboceptor organic light emission small molecule material according to claim 3, which is characterized in that step
(2) catalyst is made of palladium and three tertiary butyl phosphines.
9. the preparation method of amboceptor organic light emission small molecule material according to claim 3, which is characterized in that the step
Suddenly (2) described organic solvent is toluene.
10. any one of the claim 1~2 amboceptor organic light emission small molecule material answering in electroluminescent diode
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810035059.2A CN108250111B (en) | 2018-01-15 | 2018-01-15 | Double-receptor organic light-emitting small molecular material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810035059.2A CN108250111B (en) | 2018-01-15 | 2018-01-15 | Double-receptor organic light-emitting small molecular material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108250111A true CN108250111A (en) | 2018-07-06 |
| CN108250111B CN108250111B (en) | 2020-04-28 |
Family
ID=62726603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810035059.2A Expired - Fee Related CN108250111B (en) | 2018-01-15 | 2018-01-15 | Double-receptor organic light-emitting small molecular material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108250111B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400596A (en) * | 2018-10-30 | 2019-03-01 | 内蒙古科技大学 | A kind of oxadiazole derivatives and its application |
| CN109627233A (en) * | 2018-07-27 | 2019-04-16 | 华南理工大学 | A kind of organic photoelectrical material of azacyclic molecules and its preparation method and application replaced based on carbazole derivates |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803896A (en) * | 2015-04-28 | 2015-07-29 | 深圳市华星光电技术有限公司 | Conjugated compound containing di-(phenylsulfonyl) phenyl structure, as well as preparation method and application of conjugated compound |
| CN105254562A (en) * | 2015-09-01 | 2016-01-20 | 华南理工大学 | Organic small molecule luminescent material and organic electroluminescent device prepared from same |
| CN105873913A (en) * | 2013-09-10 | 2016-08-17 | 得克萨斯***大学评议会 | Therapeutics targeting truncated adenomatous polyposis coli (APC) proteins |
-
2018
- 2018-01-15 CN CN201810035059.2A patent/CN108250111B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105873913A (en) * | 2013-09-10 | 2016-08-17 | 得克萨斯***大学评议会 | Therapeutics targeting truncated adenomatous polyposis coli (APC) proteins |
| CN104803896A (en) * | 2015-04-28 | 2015-07-29 | 深圳市华星光电技术有限公司 | Conjugated compound containing di-(phenylsulfonyl) phenyl structure, as well as preparation method and application of conjugated compound |
| CN105254562A (en) * | 2015-09-01 | 2016-01-20 | 华南理工大学 | Organic small molecule luminescent material and organic electroluminescent device prepared from same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627233A (en) * | 2018-07-27 | 2019-04-16 | 华南理工大学 | A kind of organic photoelectrical material of azacyclic molecules and its preparation method and application replaced based on carbazole derivates |
| CN109400596A (en) * | 2018-10-30 | 2019-03-01 | 内蒙古科技大学 | A kind of oxadiazole derivatives and its application |
| CN109400596B (en) * | 2018-10-30 | 2021-09-28 | 内蒙古科技大学 | Oxadiazole derivative and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108250111B (en) | 2020-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Construction of efficient blue AIE emitters with triphenylamine and TPE moieties for non-doped OLEDs | |
| CN104844587A (en) | Conjugated compound comprising phenoxathiin structure and preparation method thereof and organic electroluminescence light emitting diode device | |
| CN108276336B (en) | Organic photoelectric functional material, light-emitting device, and preparation method and application thereof | |
| CN104803896B (en) | Contain two（Benzene sulfuryl）Conjugated compound of benzene structure and its preparation method and application | |
| CN108586318A (en) | A kind of hot activation delayed fluorescence material of solution processable and preparation method thereof | |
| CN108358919A (en) | A kind of phenanthrene derivative and its organic electroluminescence device | |
| CN107652272A (en) | It is a kind of using ketone structure as the organic compound of parent nucleus and its application in OLED | |
| CN105176521B (en) | A kind of small molecule emitter material and its application based on 1,2,3 triazole units | |
| CN111777633A (en) | Boron-containing compound and organic electroluminescent device containing same | |
| CN108164445A (en) | A kind of autonomous agent organic light emission small molecule material and its preparation method and application | |
| Chatterjee et al. | Carbazole-bridged triphenylamine-bipyridine bipolar hosts for high-efficiency low roll-off multi-color PhOLEDs | |
| CN110483576B (en) | Phosphine-containing fused heterocyclic compound and preparation method and application thereof | |
| CN106749320B (en) | A kind of benzimidazole simultaneously ketone compounds and its application in OLED device | |
| CN111499618A (en) | Compound and organic photoelectric device comprising same | |
| CN106867520B (en) | Based on heteroaromatic simultaneously -2-S, the bipolarity small molecule emitter material and its preparation method of S- dioxydibenze bithiophene unit and application | |
| CN108250111A (en) | A kind of amboceptor organic light emission small molecule material and its preparation method and application | |
| CN105481672A (en) | Series of fluorescent OLED materials | |
| CN109627255B (en) | Spiro donor organic light-emitting micromolecule material containing alkyl sulfur atom and preparation method and application thereof | |
| CN109666021A (en) | The organic light emission small molecule material and its preparation method and application of the formula donor of spiral shell containing carbonyl | |
| CN102653677B (en) | Bipolar blue-light main material and preparation method thereof and organic electroluminescent device | |
| CN110183361A (en) | ' cross ' type thermal activities delayed fluorescence material being constructed and its applying | |
| CN109134461A (en) | A kind of azepine anthracene derivant and its organic electroluminescence device | |
| CN109180559A (en) | A kind of condensed ring carbazole derivates and its organic electroluminescence device | |
| CN109180602A (en) | A kind of phenoxazine oxazine derivatives and its organic electroluminescence device | |
| CN111574535B (en) | Organic electroluminescent compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200428 |