CN107445987A - A kind of starlike amphipathic conjugated molecular material and preparation method and application - Google Patents
A kind of starlike amphipathic conjugated molecular material and preparation method and application Download PDFInfo
- Publication number
- CN107445987A CN107445987A CN201710447018.XA CN201710447018A CN107445987A CN 107445987 A CN107445987 A CN 107445987A CN 201710447018 A CN201710447018 A CN 201710447018A CN 107445987 A CN107445987 A CN 107445987A
- Authority
- CN
- China
- Prior art keywords
- compound
- starlike
- reactant
- conjugated molecular
- solvent
- 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 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 82
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010129 solution processing Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- -1 phosphonate ester Chemical class 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 26
- 239000000376 reactant Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000007641 inkjet printing Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005401 electroluminescence Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 abstract description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 abstract 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000002024 ethyl acetate extract Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4018—Esters of cycloaliphatic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
- C07F9/4059—Compounds containing the structure (RY)2P(=X)-(CH2)n-C(=O)-(CH2)m-Ar, (X, Y = O, S, Se; n>=1, m>=0)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
-
- 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
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of starlike amphipathic conjugated molecular material and preparation method and application, the material is with fluorene structured for skeleton, pyrene is end-capping group, phosphonate ester is as polarity side base, from different alkyl chains, obtained from starlike amphipathic conjugated molecular compounds, there is general structure as shown in following formula I：Wherein, R is one kind in the alkyl with phosphate, alkoxy, alkane phenyl, alkyl phenyl；Ar be benzene, triphenylamine, three and indenes in one kind.The material has the advantages such as chemical constitution is simple, synthesis cost is cheap, while has good solution processability, film forming and multifunctional light electrical characteristics, can realize the blue emission of high brightness and efficient embellishing cathode interface function simultaneously.Using the material simultaneously as luminescent layer and the Organic Light Emitting Diode of interface-modifying layer, excellent photoelectric characteristic can be realized by simplified device architecture, overcomes the technical barrier of solution processing and fabricating high-performance multilayer device.
Description
Technical field
The invention belongs to photoelectric material and applied technical field, and in particular to a kind of starlike amphipathic conjugated molecular material and its
Preparation method and application.
Background technology
Organic Light Emitting Diode (OLED) has been widely used for full color flat panel display, solid state lighting and large area flexible
The fields such as electronic device.Due to its significant progress on materials chemistry and device physics, the vacuum with sandwich construction is sunk
Product small molecule OLED comes into business application.However, vacuum deposition method manufacturing process is complicated, cost height and stock utilization
It is low.In addition, the use of shadow mask limits scalability and resolution ratio of the device in vapor deposition processes.By contrast,
The OLED of solution processing has been received significant attention with the material use of its cost-effective manufacture and low loss.
Solution processing is a kind of simple and cheap method, is more suitable for OLED large-scale production, includes spin coating, leaching
Apply, scraper for coating, ink jet printing, the processing technology such as intaglio printing and silk-screen printing.Wherein inkjet printing is all that one kind has prospect
Technology because saving material, beneficial to patterning, be easy to make large area film.Although light emitting polymer is deemed applicable to
Ink jet printing, but the charge unbalance problem in the impurity in polymer and the device based on polymer may substantially reduce effect
Rate and life-span.By contrast, small molecule structure is clear and definite, is easy to purify, it is easier to realize industrialized efficient stable device.Cause
This, it is quite attractive and in demand to manufacture small molecule OLED by ink jet printing.
However, the small molecule OLED of ink jet printing is challenging.On the one hand, commercial common OLED small molecules
Solubility and film form are all very poor generally in solution processes.On the other hand, due to interface attack phenomenon, it is difficult to printed by ink-jet
Brush builds efficient multilayer device structure with balancing charge injection and carrier transport.Therefore, exploitation has multifunctional photoelectric special
The new printable OLED material of property has especially important meaning to simplify device architecture.
The content of the invention
Technical problem：Purpose provided by the invention is a kind of starlike amphipathic conjugated molecular material and preparation method thereof with answering
With to avoid interface attack phenomenon when solwution method prepares multilayer device, and overcoming current solution processing Organic Light Emitting Diode
The problems such as device architecture complexity, electron injecting layer solution processing difficulties.
Technical scheme：To achieve the above object, the technical solution adopted by the present invention is：
A kind of starlike amphipathic conjugated molecular material, for the material with fluorene structured for skeleton, pyrene is end-capping group, and phosphonate ester is made
For polarity side base, from different alkyl chains, and obtained starlike amphipathic conjugated molecular compounds, have as shown in following formula I
General structure：
Wherein, the one kind of core Ar in such as structure of following formula II：
In formula II, R ' is one kind in C1-C30 alkyl, alkoxy, alkane phenyl, alkane phenoxy group, aryl；* it is connection position
Put；
One kind of side base R structures heteroaryl structure in following formula III：
In formula III, 1≤n≤20, n are natural number.
Specifically, the material is any shown compound of following formula IV, V, VI, VII：
The preparation method of the starlike amphipathic conjugated molecular material of the present invention, comprising two kinds of synthetic routes and synthesis step,
The first synthetic route and synthesis step are：
Side base R ' structures are:Wherein 1≤n≤20, n are natural number；
Side base R structures are：Wherein 1≤n≤20, n are natural number；
The one kind of core Ar in the structure as shown in following formula II：
In formula II, R ' is C1-C30 alkyl；
Reactant (a), reactant (b) and smelling of tetrabutyl ammonium, potassium carbonate are added in reaction vessel by step (1), are added
Entering solvent makes its dissolving, reacts 4-12h under counterflow condition, obtains compound (c)；
Step (2) is by the product Compound (c) of step (1), compound (d), TBAB and four triphenylphosphines
Palladium is added in reaction vessel, and adding solvent makes its dissolving, under nitrogen protection, 95 DEG C of reaction 12h, obtains compound (e)；
Step (3) adds the product Compound (e) of step (2), compound (f), TBAB, tetra-triphenylphosphine palladium
Enter and dissolved into microwave tube in a solvent, react 0.5-1h at 100-150 DEG C in microwave reactor, obtain compound (g)；Step
Suddenly the product Compound (g) of step (3), triethyl phosphite are added in microwave tube and dissolved in a solvent by (4), anti-in microwave
Answer in device and react 0.5-1h at 100-150 DEG C, obtain compound (h).
The solvent used in the step (1) is acetone or potassium hydroxide aqueous solution, reactant (a) and reactant (b)
Mol ratio is 1：(3-10)；
The solvent used in the step (2) is the one or more in tetrahydrofuran, toluene, chlorobenzene, o-dichlorohenzene, is changed
Compound (c)：Reactant (d)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(0.8-1.2):(0.1-0.2)：
(0.03-0.05)；
The solvent used in the step (3) is the one or more in tetrahydrofuran, toluene, chlorobenzene, o-dichlorohenzene, instead
Answer thing (f)：Compound (e)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(3-5):(0.3-0.6)：(0.05-
0.15)；
In the step (4), the mol ratio of compound (g) and triethyl phosphite is 1:(60-90).
Second of synthetic route and synthesis step are：
Side base R ' structures are:Wherein 1≤n≤20, n are natural number；
Side base R structures are：Wherein 1≤n≤20, n are natural number；
The one kind of core Ar in the structure as shown in following formula II：
In formula II, R ' is C1-C30 alkyl；
Step (1) is by reactant (a), reactant (b), pyrovinic acid, and into reaction vessel, adding solvent makes its dissolving,
36-48h is reacted under counterflow condition, obtains compound (c)；
The product Compound (c) of step (1), reactant (d) and smelling of tetrabutyl ammonium, potassium carbonate are added to by step (2)
In reaction vessel, adding solvent makes its dissolving, reacts 4-12h under counterflow condition, obtains compound (e)；
Step (3) is by the product Compound (e) of step (2), compound (f), TBAB and four triphenylphosphines
Palladium is added in reaction vessel, and adding solvent makes its dissolving, under nitrogen protection, 95 DEG C of reaction 12h, obtains compound (g)；
Step (4) adds the product Compound (g) of step (3), compound (h), TBAB, tetra-triphenylphosphine palladium
Enter and dissolved into microwave tube in a solvent, react 0.5-1h at 100-150 DEG C in microwave reactor, obtain compound (i)；
The product Compound (i) of step (4), triethyl phosphite are added in microwave tube by step (5) is dissolved in solvent
In, 0.5-1h is reacted at 100-150 DEG C in microwave reactor, obtains compound (j).
The solvent used in the step (1) is chloroform；
The solvent used in the step (2) is acetone or potassium hydroxide aqueous solution, reactant (c) and reactant (d)
Mol ratio is 1：(3-10)；
The solvent used in the step (3) is the one or more in tetrahydrofuran, toluene, chlorobenzene, o-dichlorohenzene, is changed
Compound (e)：Reactant (f)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(0.8-1.2):(0.1-0.2)：
(0.03-0.05)；
The solvent used in the step (4) is the one or more in tetrahydrofuran, toluene, chlorobenzene, o-dichlorohenzene, instead
Answer thing (h)：Compound (g)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(3-5):(0.3-0.6)：(0.05-
0.15)；
In the step (5), the mol ratio of compound (i) and triethyl phosphite is 1:(60-90).
The multi-functional starlike amphipathic conjugated molecular material of the present invention, is applied to organic electroluminescence separately as electron injecting layer
In luminescent device, its structure is：Anode/luminescent layer/electron injecting layer/negative electrode；Based on such amphipathic conjugation small molecule material
Single layer organic electroluminescent device, the material can be used as luminescent layer and electron injecting layer simultaneously, and its structure is：Anode/hair
Photosphere/negative electrode.
The multi-functional starlike amphipathic conjugated molecular material of the present invention, has alcohol-soluble, can be processed by solution and prepare list
Layer or multilayer organic light emitting diode device, including two kinds of means of spin coating and inkjet printing.
Beneficial effect：The multi-functional starlike amphipathic conjugated molecular material of the present invention, with fluorene structured for skeleton, pyrene is as end
Base, phosphate is as polarity side base.Be coupled by Suzuki, a series of processes such as phosphating reaction have synthesized such material,
The material has the advantages such as building-up process is simple and easy to control, cost is cheap, be easily purified, yield height.The combination of pyrene and fluorenes assigns small
The good heat endurance of molecule, high fluorescence quantum efficiency and excellent luminosity, phosphate polar group then assign material
Excellent alcohol-soluble, electron injection ability and filming performance.The material is applied to the processing modes such as spin coating, inkjet printing, energy
Orthogonal dissolution characteristics are formed so as to avoid interface attack with regular activated layer solvent, can realize efficient blue emission simultaneously and have
The embellishing cathode interface function of effect, device architecture can be simplified while obtain efficient device performance.
Brief description of the drawings
Fig. 1 is the compound PH-FEP's in embodiment 11H NMR spectras.
Fig. 2 is the compound PH-FEP's in embodiment 113C NMR spectras.
Fig. 3 is the compound TPA-FEP's in embodiment 11HNMR spectrograms.
Fig. 4 is the compound TPA-FEP's in embodiment 113C NMR spectras.
Fig. 5 is the compound PH-OEP's in embodiment 21H NMR spectras.
Fig. 6 is the compound PH-OEP's in embodiment 213C NMR spectras.
Fig. 7 is the compound TPA-OEP's in embodiment 21H NMR spectras.
Fig. 8 is the compound TPA-OEP's in embodiment 213C NMR spectras.
Fig. 9 is compound PH-FEP/PH-FEP/PH-FEP/PH-FEP (a) solution state and (b) thin-film state UV absorption
Spectrogram.
Figure 10 is compound PH-FEP/PH-FEP/PH-FEP/PH-FEP (a) solution state and (b) thin-film state fluorescent emission
Spectrogram.
Figure 11 is the Current efficiency-voltage curve of the Organic Light Emitting Diode in embodiment 3.
Embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1：
Synthetic route is as follows：
Comprise the following steps that：
Ith step：2,7- dibromo fluorenes (20g, 61.7mmol), 1,6- dibromo-hexane (35.5mL, 246.9mmol), the tetrabutyl
The mass concentration that ammonium bromide (TBAB) (2g) adds 50g is in 50% potassium hydroxide aqueous solution, and 65 DEG C of reactions are overnight.Extraction, rotation
Dry, 100~200 mesh cross post, obtain 32g compound A, yield 160%.
IIth step：After compound A (1g, 1.54mmol), 1- boric acid fat pyrene (0.421g, 1.28mmol) substitute nitrogen three times
TBAB (TBAB) (0.099g, 0.31mmol) is added, substitutes nitrogen, lucifuge adds catalyst Pd (PPh3)4
(0.089g, 0.077mmol) is dissolved in 21mL toluene and 7mL wet chemical, and 95 DEG C are reacted 12 hours.DCM extracts
Take and be spin-dried for pillar, obtain compound B, yield 76%.
IIIth step：Compound B (0.304g, 0.395mmol), 1,3,5- tri- boric acid fat are sequentially added in 10ml microwave tubes
Benzene (0.040g, 0.088mmol), TBAB (TBAB) (0.017g, 0.053mmol) and Pd (PPh3)4(0.015g,
0.013mmol), under conditions of sealing, lucifuge, nitrogen is substituted.Add the mixed solution that 5mL has fully used nitrogen bubble
(according to volume ratio, tetrahydrofuran solution：Concentration is 2M K2CO3The aqueous solution=3:1) it is added in reaction system.It is sufficiently stirred
Afterwards, under 250W power conditions, microwave radiation technology reaction 30min.Ethyl acetate extracts, and was spin-dried for pillar, and obtained presoma PH-F.
It is computed, yield 49%.
IVth step：Presoma PH-F (0.20g, 0.093mmol) is put into microwave tube, is added in excessive triethyl phosphite
Solution be heated to 140 DEG C holding 1h.Then unnecessary triethyl phosphite is removed with the method distilled in vacuum.Finally, pass through
Chromatogram purification is crossed (according to volume ratio, dichloromethane：Tetrahydrofuran makees=3：1 is eluent) obtain white compound PH-FEP
(0.127g, 63%).
Vth step：Compound B (0.278g, 0.361mmol), three boric acid of triphenylamine are sequentially added in 10ml microwave tubes
Fat (0.05g, 0.08mmol) TBAB (0.015g, 0.048mmol) and Pd (PPh3)4(0.014g, 0.012mmol), close
Under conditions of envelope, lucifuge, nitrogen is substituted.5mL is added fully with the mixed solution of nitrogen bubble (according to volume ratio, tetrahydrochysene
Tetrahydrofuran solution：Concentration is 2M K2CO3The aqueous solution=3:1) it is added in reaction system.After being sufficiently stirred, in 250W power conditions
Under, microwave radiation technology reaction 30min.Ethyl acetate extracts, and was spin-dried for pillar, and obtained presoma TPA-F, yield 43%.
VIth step：Presoma TPA-F (0.20g, 0.086mmol) is put into microwave tube, adds excessive triethyl phosphite
In solution be heated to 140 DEG C holding 1h.Then unnecessary triethyl phosphite is removed with vacuum distillation method, in chromatogram purification
(according to volume ratio, dichloromethane：Tetrahydrofuran makees=3：1 is eluent) obtain afterwards compound TPA-FEP (0.143g,
72%) greenish yellow solid, is obtained.
Compound B:1H NMR(400MHz,CDCl3):δ8.31–8.17(m,4H),8.17–7.98(m,5H),7.90–
7.83 (m, 1H), 7.74-7.42 (m, 5H), 3.31 (t, J=6.8Hz, 4H), 2.11-1.93 (m, 4H), 1.79-1.66 (m,
4H), 1.26 (dd, J=14.8,7.1Hz, 4H), 1.21-1.09 (m, 4H), 0.88-0.72 (m, 4H)13C NMR(100MHz,
CDCl3):δ151.69,150.82,143.05,140.63,140.43,140.26,131.56,131.01,130.65,
129.69,128.64,127.72,127.56,127.50,126.74,126.14,125.43,125.25,124.91,124.75,
121.85,55.42,40.40,34.00,32.74,29.74,29.26,27.94,23.94.MS m/z:771.06(M+)
(calcd:771.48).Elemental Analysis:(the calcd of C 77.53%, H 6.47%:C 77.63%, H
6.43%)
Compound PH-F:1H NMR(400MHz,CDCl3):δ 8.29 (dd, J=8.5,6.8Hz, 6H), 8.23 (t, J=
7.3Hz, 6H), 8.13 (dd, J=11.7,3.0Hz, 11H), 8.03 (ddd, J=12.2,10.9,5.3Hz, 13H), 7.92
(dd, J=7.9,1.1Hz, 3H), 7.84 (s, 3H), 7.70 (dd, J=9.9,2.1Hz, 6H), 3.32 (d, J=6.8Hz,
12H), 2.18 (dd, J=9.6,6.2Hz, 12H), 1.81-1.70 (m, 12H), 1.35 (d, J=7.7Hz, 6H), 1.28 (s,
6H), 1.23 (dd, J=14.6,7.5Hz, 12H), 0.94 (dd, J=15.7,8.1Hz, 12H)13C NMR(100MHz,
CDCl3):δ151.69,150.82,143.05,140.63,140.43,140.26,139.90,138.13,131.56,
131.01,130.65,129.69,128.64,127.72,127.56,127.50,126.74,126.14,125.43,125.37,
125.25,125.14,124.99,124.91,124.75,121.85,120.41,119.99,55.42,40.40,34.00,
32.74,29.74,29.26,27.94,23.94.MS m/z:2148.43(M+)(calcd:2149.80)
.ElementalAnalysis:(the calcd of C 72.11%, H 5.66%:C 72.07%, H 5.63%)
Compound TPA-F:1H NMR(400MHz,CDCl3):δ 8.24 (ddd, J=19.4,11.5,7.7Hz, 12H),
8.16-8.01 (m, 15H), 7.91 (dd, J=17.9,7.8Hz, 6H), 7.67 (ddd, J=13.8,9.5,6.0Hz, 18H),
7.38 (d, J=8.6Hz, 6H), 3.32 (t, J=6.8Hz, 12H), 2.19-2.02 (m, 12H), 1.80-1.67 (m, 12H),
1.29 (dd, J=15.0,7.6Hz, 12H), 1.19 (dd, J=14.6,7.4Hz, 12H), 0.89 (dt, J=12.1,6.8Hz,
12H).13C NMR(100MHz,CDCl3):δ151.49,150.78,146.85,140.02,139.92,139.67,138.21,
136.06,131.56,131.02,130.62,129.59,128.65,128.02,127.68,127.49,126.09,125.87,
125.27,125.19,125.14,125.00,124.86,124.71,124.57,120.96,120.27,119.76,55.27,
40.34,33.94,32.71,29.17,27.87,23.86.MS m/z:2317.64(M+)(calcd:2317.01)
.Elemental Analysis:(the calcd of C 73.00%, H 5.65%, N 0.58%:C 73.09%, H 5.61%, N
0.60%)
Target product PH-FEP:1H NMR(400MHz,CDCl3):δ 8.25 (dt, J=15.2,8.0Hz, 12H), 8.15-
7.96 (m, 24H), 7.88 (d, J=8.1Hz, 3H), 7.80 (s, 3H), 7.70-7.64 (m, 6H), 4.01 (qd, J=7.0,
3.1Hz, 24H), 2.22-2.09 (m, 12H), 1.68-1.59 (m, 12H), 1.49 (dd, J=14.6,8.2Hz, 12H), 1.29-
1.17(m,72H).13C NMR(100MHz,CDCl3):δ151.73,150.87,142.98,140.61,140.28,139.91,
138.16,131.55,131.01,130.62,129.64,128.62,127.70,127.47,126.68,126.10,125.82,
121.72,120.38,119.93,107.89,77.30,77.04,76.72,67.63,61.36,55.43,40.54,30.51,
29.53,29.17,26.32,24.92,23.98,22.46,16.44.MS m/z:2492.05(M+),2515.14([M+Na]+)
(calcd:2492.95).ElementalAnalysis:(the calcd of C 73.82%, H 7.20%:C 73.72%, H
7.28%)
Target product TPA-FEP:1H NMR(400MHz,CDCl3):δ 8.24 (dt, J=21.7,7.7Hz, 12H), 8.17-
7.99 (m, 15H), 7.91 (dd, J=17.5,7.8Hz, 6H), 7.77-7.57 (m, 18H), 7.38 (d, J=7.9Hz, 6H),
4.03 (dd, J=10.6,6.9Hz, 24H), 1.56-1.38 (m, 36H), 1.24 (dd, J=18.9,12.0Hz, 72H)13C
NMR(100MHz,CDCl3):δ151.43,146.82,138.24,135.93,131.56,131.02,130.59,128.57,
128.01,127.70,127.47,126.08,125.84,125.20,124.85,124.55,120.93,120.25,77.38,
77.06,76.74,61.42,55.29,40.51,30.43,29.65,26.27,24.88,16.42.MS m/z:2660.19(M+),2683.57(M+Na+)(calcd:2660.16).Elemental Analysis:C 74.55%, H 7.13%, N
0.50% (calcd:C 74.50%, H 7.16%, N0.53%)
Embodiment 2：
Synthetic route is：
Comprise the following steps that：
Ith step：2,7- dibromo fluorenones (30.3g, 89.65mmol) are placed in 500mL there-necked flasks, addition phenol (71mL,
591.18mmol), 20mL pyrovinic acid, 120mL CCl4, temperature is adjusted to 80 DEG C, reacts 42h.Stop reaction, used after cooling
K2CO3Solution is quenched, should be slow during addition, have a large amount of bubbles and produce.After filter, waste liquid is purple.With more washings of DCM
To it is powdered be lily compound C about 28g, yield 93%.
IIth step：Compound C (10g, 19.67mmol), 1,6- dibromo-hexane (19.20g, 78.71mmol), the tetrabutyl is smelt
Change ammonium (TBAB) (2g) to add in 50g 50% potassium hydroxide aqueous solution, 65 DEG C of reactions are overnight.Extraction, is spin-dried for, 100~200 mesh
Cross post.Obtain 13.2g compound D, yield 132%.
IIIth step：Compound D (1g, 1.199mmol), 1- boric acid fat pyrene (0.328g, 1mmol) are substituted nitrogen and added afterwards three times
Enter smelling of tetrabutyl ammonium (TBAB) (0.077g, 0.240mmol), substitute nitrogen, lucifuge adds catalyst Pd (PPh3)4
(0.069g, 0.060mmol) is dissolved in 15mL toluene and 5mL wet chemical.95 DEG C, react 12 hours.Use DCM
Extraction, was spin-dried for pillar, and obtained compound E, yield about 63%.
IVth step：Compound E (0.377g, 0.395mmol), three boric acid fat of benzene are sequentially added in 10mL microwave tubes
(0.040g, 0.088mmol), smelling of tetrabutyl ammonium (TBAB) (0.017g, 0.053mmol) and Pd (PPh3)4(0.015g,
0.013mmol), sealing, lucifuge, substitute nitrogen.Add 5mL fully with the mixed solution of nitrogen bubble (according to volume ratio,
Tetrahydrofuran solution：Concentration is 2M K2CO3The aqueous solution=3:1) it is added in reaction system.After being sufficiently stirred, in 250W power
Under the conditions of, microwave radiation technology reaction 30min.Ethyl acetate extracts, and was spin-dried for pillar, and obtained presoma PH-O, yield 53%.
Vth step：Solution of the presoma PH-O (0.20g, 0.074mmol) in triethyl phosphite is heated to 140 DEG C of guarantors
Hold 72h.Then, unnecessary triethyl phosphite is removed using the method being distilled in a vacuum.Finally, with chromatogram purification (according to
Volume ratio, dichloromethane：Tetrahydrofuran makees=1：1 is eluent) method obtain white compound PH-OEP (0.139g,
70%).
VIth step：Compound E (0.345g, 0.361mmol), three boric acid of triphenylamine are sequentially added in 10ml microwave tubes
Fat (0.05g, 0.08mmol), TBAB (0.015g, 0.048mmol) and Pd (PPh3)4(0.014g, 0.012mmol), close
Under conditions of envelope, lucifuge, nitrogen is substituted.5mL is added fully with the mixed solution of nitrogen bubble (according to volume ratio, tetrahydrochysene
Tetrahydrofuran solution：Concentration is 2M K2CO3The aqueous solution=3:1) it is added in reaction system.After being sufficiently stirred, in 250W power conditions
Under, microwave radiation technology reaction 30min.Ethyl acetate extracts, and was spin-dried for pillar, and obtained presoma TPA-O, yield 43%.
VIIth step：Solution of the TPA-O (0.20g, 0.070mmol) in triethyl phosphite is heated to 140 DEG C of holdings
72h.Then unnecessary triethyl phosphite is removed with vacuum distillation method, finally, with chromatogram purification (according to volume ratio, dichloromethane
Alkane：Tetrahydrofuran makees=1：1 is eluent) obtain yellow greenish powder compound TPA-OEP (0.139g, 70%).
Compound E:1H NMR(400MHz,CDCl3):δ8.25–8.11(m,4H),8.08(s,2H),8.05–7.93(m,
3H), 7.89 (d, J=7.7Hz, 1H), 7.75-7.60 (m, 3H), 7.59-7.50 (m, 2H), 7.18 (d, J=8.6Hz, 4H),
6.78 (d, J=8.6Hz, 4H), 3.91 (t, J=6.3Hz, 4H), 3.40 (t, J=6.8Hz, 4H), 1.92-1.82 (m, 4H),
1.75 (d, J=5.9Hz, 4H), 1.48 (d, J=3.1Hz, 8H)13C NMR(100MHz,CDCl3):δ158.02,154.12,
152.03,140.92,138.78,137.97,137.56,137.19,131.50,130.92,130.73,130.64,130.11,
129.44,129.18,128.46,128.39,127.66,127.51,127.42,126.08,125.19,125.04,124.90,
124.83,124.67,121.67,121.48,120.17,114.27,67.66,64.46,33.86,32.69,29.11,
27.93,25.33.MS m/z:955.43(M+)(calcd:955.67).ElementalAnalysis:C 66.50%, H
4.92%, (calcd:C 66.61%, H 4.96%)
Compound PH-O:1H NMR(400MHz,CDCl3):δ8.24–8.15(m,12H),8.10(s,6H),7.99(ddd,
J=13.9,13.0,7.6Hz, 15H), 7.80-7.66 (m, 15H), 7.29 (s, 12H), 6.78 (d, J=8.8Hz, 12H),
3.90 (t, J=6.2Hz, 12H), 3.37 (t, J=6.8Hz, 12H), 1.84 (dd, J=12.9,6.1Hz, 12H), 1.79-
1.72(m,12H),1.50–1.43(m,24H).13C NMR(100MHz,CDCl3):δ157.92,142.47,140.59,
129.29,127.47,114.23,67.65,33.84,32.69,31.95,29.73,29.14,27.93,25.34,22.69.MS
m/z:2699.23(M+)(calcd:2702.39).ElementalAnalysis:(the calcd of C 73.30%, H 5.34%:C
73.34%, H 5.37%)
Compound TPA-O:1H NMR(400MHz,CDCl3):δ8.24–8.14(m,12H),8.09(s,6H),7.97
(ddd, J=30.1,16.6,8.2Hz, 15H), 7.69 (d, J=17.1Hz, 12H), 7.54 (d, J=8.6Hz, 6H), 7.28
(s, 6H), 7.22 (d, J=8.5Hz, 6H), 6.79 (d, J=8.8Hz, 12H), 3.91 (t, J=6.3Hz, 12H), 3.39 (t, J
=6.8Hz, 12H), 1.92-1.73 (m, 24H), 1.53-1.44 (m, 24H)13C NMR(100MHz,CDCl3):δ157.87,
152.82,152.49,146.72,140.37,140.11,139.32,138.83,138.66,137.99,137.83,135.75,
131.52,130.96,130.58,130.02,129.31,128.52,128.43,127.95,127.74,127.45,126.21,
126.05,125.35,125.15,125.07,124.94,124.79,124.68,124.38,120.66,120.10,114.18,
67.65,64.46,33.85,32.69,31.96,31.47,30.21,29.73,29.47,29.13,27.93,25.34,
22.73.MS m/z:2869.77(M+)(calcd:2869.60).ElementalAnalysis:C 73.98%, H 5.40%,
(the calcd of N 0.53%:C 74.09%, H 5.37%, N 0.49%)
Target product PH-OEP:1H NMR(400MHz,CDCl3):δ8.21(s,12H),8.10(s,6H),8.00(s,
15H), 7.74 (d, J=21.3Hz, 15H), 7.27 (s, 15H), 6.79 (s, 12H), 4.05 (s, 24H), 3.90 (s, 12H),
1.67 (d, J=54.2Hz, 36H), 1.44 (s, 24H), 1.27 (s, 36H)13C NMR(100MHz,CDCl3):δ157.97,
142.51,140.63,139.34,138.67,137.84,131.53,130.97,130.61,130.04,129.29,128.45,
127.60,126.04,124.95,114.25,77.35,77.03,76.72,64.58,61.25,30.34,29.12,26.24,
25.65,24.92,16.48.MS m/z:3045.82(M+),3068.92([M+Na]+)(calcd:3045.53).Elemental
Analysis:(the calcd of C 74.62%, H 6.71%:C 74.54%, H 6.75%)
Target product TPA-OEP:1H NMR(400MHz,CDCl3):δ 8.19 (dd, J=16.3,9.3Hz, 12H), 8.12-
7.82 (m, 21H), 7.68 (d, J=15.3Hz, 12H), 7.54 (d, J=7.8Hz, 6H), 7.26 (t, J=7.6Hz, 18H),
6.79 (d, J=8.2Hz, 12H), 4.06 (dd, J=13.7,6.9Hz, 24H), 3.90 (s, 12H), 1.78-1.58 (m, 36H),
1.32 (dd, J=37.4,30.5Hz, 60H)13C NMR(100MHz,CDCl3):δ157.89,152.82,152.53,
146.72,140.36,140.13,138.73,137.90,135.75,133.14,131.52,130.97,130.57,130.00,
129.30,128.47,127.94,127.58,126.13,125.48,124.37,120.64,120.06,114.17,67.70,
64.46,61.36,30.23,29.08,26.33,25.64,24.93,22.36,16.45.MS m/z:3212.76(M+)
(calcd:3212.74).Elemental Analysis:(the calcd of C 75.06%, H 6.75%, N 0.47%:C
75.14%, H 6.68%, N 0.44%)
Embodiment 3
The preparation of Organic Light Emitting Diode.
OLEDs single layer devices are prepared by spin-coating method：Its device architecture is ITO/PEDOT:PSS 35nm/ luminescent layers
65nm/Al 80nm.Solvent is done using chloroform, luminescent layer, which is used in compound TPA-FEP/PH-FEP/TPA-OEP/PH-OEP, appoints
Meaning is a kind of, prepares 15mg/mL solution.The lower spin coating of nitrogen protection, rotating speed 1500rpm, 80 DEG C of annealing 10min.
Contrasted below for the electroluminescent properties of above-mentioned three kinds of individual layer organic light emitting diode devices：
aIt is 1cdm to open bright voltage and be defined as brightness-2When operating voltage.bDuring high-high brightness.
Four single layer devices are to use the amphiphilic conjugated molecule of star topology while be used as illuminator and cathode interface layer.
The device performance in form is analyzed, the device A current efficiency based on material TPA-OEP is up to 0.69cdA-1, better than TPA-
FEP 0.45cdA-1, PH-FEP 0.32cdA-1And PH-OEP 0.43cdA-1.Wherein, device A high-high brightness reaches
5701.6cd m-2, open-circuit voltage only 4.5V.It can directly act in the aluminium electrode of high work function, illustrate that the material has very well
Cathodic modification ability.Result above absolutely proves that this novel MOLECULE DESIGN is advantageous to real by simple device architecture
Existing excellent photoelectric characteristic.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other any without departing from the modifications and variations done under principles of the invention, equivalent substitute mode is should be, is all wrapped
Containing within the scope of the present invention.
Claims (10)
- A kind of 1. starlike amphipathic conjugated molecular material, it is characterised in that：For the material with fluorene structured for skeleton, pyrene is END CAPPED GROUP Group, phosphonate ester is used as polarity side base, from different alkyl chains, and obtained starlike amphipathic conjugated molecular compounds, with such as General structure shown in following formula I：Wherein, the one kind of core Ar in such as structure of following formula II：In formula II, R ' is one kind in C1-C30 alkyl, alkoxy, alkane phenyl, alkane phenoxy group, aryl；* it is link position；One kind of side base R structures heteroaryl structure in following formula III：In formula III, 1≤n≤20, n are natural number.
- 2. starlike amphipathic conjugated molecular material as claimed in claim 1, it is characterised in that：The material be following formula IV, V, VIth, VII any shown compound：
- A kind of 3. preparation method of starlike amphipathic conjugated molecular material as claimed in claim 1 or 2, it is characterised in that：Bag Containing following synthetic route and synthesis step：Side base R ' structures are:Wherein 1≤n≤20, n are natural number；Side base R structures are：Wherein 1≤n≤20, n are natural number；The one kind of core Ar in the structure as shown in following formula II：In formula II, R ' is C1-C30 alkyl；Reactant (a), reactant (b) and smelling of tetrabutyl ammonium, potassium hydroxide aqueous solution are added to reaction vessel by step (1) In, adding solvent makes its dissolving, reacts 4-12h under counterflow condition, obtains compound (c)；Step (2) adds the product Compound (c) of step (1), compound (d), TBAB and tetra-triphenylphosphine palladium Enter into reaction vessel, adding organic solvent and wet chemical makes its dissolving, under nitrogen protection, 95 DEG C of reaction 12h, obtains Compound (e)；The product Compound (e) of step (2), compound (f), TBAB, tetra-triphenylphosphine palladium are added to by step (3) Dissolved in microwave tube in a solvent, react 0.5-1h at 100-150 DEG C in microwave reactor, obtain compound (g)；Step (4) product Compound (g) of step (3), triethyl phosphite are added in microwave tube and dissolved in a solvent, in microwave reaction 0.5-1h is reacted at 100-150 DEG C in device, obtains compound (h).
- 4. the preparation method of starlike amphipathic conjugated molecular material as claimed in claim 3, it is characterised in that：The solvent used in the step (1) is mole of acetone or potassium hydroxide aqueous solution, reactant (a) and reactant (b) Than for 1：(3-10).
- 5. the preparation method of starlike amphipathic conjugated molecular material as claimed in claim 3, it is characterised in that：The step (2) solvent used in is tetrahydrofuran, the one or more in toluene, chlorobenzene, o-dichlorohenzene, compound (c)：Reactant (d)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(0.8-1.2):(0.1-0.2)：(0.03-0.05).
- 6. the preparation method of starlike amphipathic conjugated molecular material as claimed in claim 3, it is characterised in that：The step (3) solvent used in is tetrahydrofuran, the one or more in toluene, chlorobenzene, o-dichlorohenzene, reactant (f)：Compound (e)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(3-5):(0.3-0.6)：(0.05-0.15)；In the step (4), the mol ratio of compound (g) and triethyl phosphite is 1:(60-90).
- A kind of 7. preparation method of starlike amphipathic conjugated molecular material as claimed in claim 1 or 2, it is characterised in that：Bag Containing following synthetic route and synthesis step：Side base R ' structures are:Wherein 1≤n≤20, n are natural number；Side base R structures are：Wherein 1≤n≤20, n are natural number；The one kind of core Ar in the structure as shown in following formula II：In formula II, R ' is C1-C30 alkyl；Step (1) is by reactant (a), reactant (b), pyrovinic acid, and into reaction vessel, adding solvent makes its dissolving, flows back Under the conditions of react 36-48h, obtain compound (c)；The product Compound (c) of step (1), reactant (d) and smelling of tetrabutyl ammonium, potassium carbonate are added to reaction by step (2) In container, adding solvent makes its dissolving, reacts 4-12h under counterflow condition, obtains compound (e)；Step (3) adds the product Compound (e) of step (2), compound (f), TBAB and tetra-triphenylphosphine palladium Enter into reaction vessel, adding solvent makes its dissolving, under nitrogen protection, 95 DEG C of reaction 12h, obtains compound (g)；The product Compound (g) of step (3), compound (h), TBAB, tetra-triphenylphosphine palladium are added to by step (4) Dissolved in microwave tube in a solvent, react 0.5-1h at 100-150 DEG C in microwave reactor, obtain compound (i)；Step (5) product Compound (i) of step (4), triethyl phosphite are added in microwave tube dissolve in a solvent, 0.5-1h is reacted at 100-150 DEG C in microwave reactor, obtains compound (j).
- 8. the preparation method of starlike amphipathic conjugated molecular material as claimed in claim 7, it is characterised in that：The solvent used in the step (1) is chloroform；The solvent used in the step (2) is mole of acetone or potassium hydroxide aqueous solution, reactant (c) and reactant (d) Than for 1：(3-10)；The solvent used in the step (3) is tetrahydrofuran, the one or more in toluene, chlorobenzene, o-dichlorohenzene, compound (e)：Reactant (f)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(0.8-1.2):(0.1-0.2)：(0.03- 0.05)；The solvent used in the step (4) is tetrahydrofuran, the one or more in toluene, chlorobenzene, o-dichlorohenzene, reactant (h)：Compound (g)：TBAB：The mol ratio of tetra-triphenylphosphine palladium is 1:(3-5):(0.3-0.6)：(0.05- 0.15)；In the step (5), the mol ratio of compound (i) and triethyl phosphite is 1:(60-90).
- A kind of 9. starlike amphipathic conjugated molecular material as claimed in claim 1 or 2 answering in organic electroluminescence device With.
- 10. application as claimed in claim 7, it is characterised in that：The material is separately as electron injecting layer, or is used as hair simultaneously Photosphere is applied to organic electroluminescence device with electron injecting layer, and the organic electroluminescence device uses Solution processing techniques system Form, Solution processing techniques are spin coating or inkjet printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710447018.XA CN107445987B (en) | 2017-06-14 | 2017-06-14 | Star-shaped amphiphilic conjugated molecular material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710447018.XA CN107445987B (en) | 2017-06-14 | 2017-06-14 | Star-shaped amphiphilic conjugated molecular material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107445987A true CN107445987A (en) | 2017-12-08 |
| CN107445987B CN107445987B (en) | 2020-07-07 |
Family
ID=60487008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710447018.XA Active CN107445987B (en) | 2017-06-14 | 2017-06-14 | Star-shaped amphiphilic conjugated molecular material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107445987B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832003A (en) * | 2018-06-14 | 2018-11-16 | 南京邮电大学 | A method of improving perovskite solar cell photoelectric transfer efficiency |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747208A (en) * | 2009-12-29 | 2010-06-23 | 浙江工业大学 | Non-conjugated derivative material with fluorine-triphenylamine structure and synthesis method thereof |
| CN102911204A (en) * | 2012-10-26 | 2013-02-06 | 华南理工大学 | Phosphate group based small-molecule water/alcohol soluble material and preparation method and application thereof |
| CN103951813A (en) * | 2014-03-31 | 2014-07-30 | 南京邮电大学 | 9-Aryl substituted flourenyl conjugated polyelectrolyte, and preparation method and application thereof |
| CN105566124A (en) * | 2015-09-29 | 2016-05-11 | 南京邮电大学 | Diaryl fluorene porous organic photoelectric semiconductor material, preparation method and applications thereof |
| CN105924471A (en) * | 2016-05-03 | 2016-09-07 | 南京邮电大学 | Open-loop fullerene interface modification material, and preparation method and application thereof |
-
2017
- 2017-06-14 CN CN201710447018.XA patent/CN107445987B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747208A (en) * | 2009-12-29 | 2010-06-23 | 浙江工业大学 | Non-conjugated derivative material with fluorine-triphenylamine structure and synthesis method thereof |
| CN102911204A (en) * | 2012-10-26 | 2013-02-06 | 华南理工大学 | Phosphate group based small-molecule water/alcohol soluble material and preparation method and application thereof |
| CN103951813A (en) * | 2014-03-31 | 2014-07-30 | 南京邮电大学 | 9-Aryl substituted flourenyl conjugated polyelectrolyte, and preparation method and application thereof |
| CN105566124A (en) * | 2015-09-29 | 2016-05-11 | 南京邮电大学 | Diaryl fluorene porous organic photoelectric semiconductor material, preparation method and applications thereof |
| CN105924471A (en) * | 2016-05-03 | 2016-09-07 | 南京邮电大学 | Open-loop fullerene interface modification material, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHEN D C. ET AL: ""Solution-processed cathode-interlayer-free deep blue organic light-emitting diodes"", 《ORGANIC ELECTRONICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832003A (en) * | 2018-06-14 | 2018-11-16 | 南京邮电大学 | A method of improving perovskite solar cell photoelectric transfer efficiency |
| CN108832003B (en) * | 2018-06-14 | 2022-06-03 | 南京邮电大学 | Method for improving photoelectric conversion efficiency of perovskite solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107445987B (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103833507B (en) | A series of electroluminescent organic materials and preparation method and application | |
| CN104761547A (en) | Thioxanthone-aromatic amine compound and organic light-emitting device using same | |
| CN100548984C (en) | A kind of indoles [3,2-b] carbazole derivative organic electroluminescent material | |
| CN104910372B (en) | Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application | |
| CN107827807A (en) | A kind of derivative containing carbazole structure and preparation method thereof and organic electroluminescence device | |
| CN106543123B (en) | A kind of anthracene compound and preparation method thereof and organic luminescent device | |
| CN102838442A (en) | 9-alkenylfluorene derivatives and application thereof | |
| CN110272421A (en) | A kind of general formula compound and its application | |
| CN109734608A (en) | A kind of organic compound and its organic electroluminescence device using the compound | |
| CN106749094A (en) | 42 (2` hydroxy phenyls) benzoxazole compounds and its preparation method and purposes containing substituted base | |
| CN105968104A (en) | Luminescent material and preparation method thereof and organic light emitting diode using same | |
| CN103739607A (en) | Tri-carbazole multi-arm structural red-light--emitting material and preparation method and application thereof | |
| CN101166383B (en) | Compound for organic EL device and organic EL device | |
| CN105481901A (en) | Iridium-containing red metal complex, preparation method thereof, and organic electroluminescent device adopting complex | |
| CN101910357A (en) | Blue electroluminescent compounds with high efficiency and display device using the same | |
| CN107445987A (en) | A kind of starlike amphipathic conjugated molecular material and preparation method and application | |
| CN104177603B (en) | Hyperbranched white light polymer with spiro-bisfluorene as core and preparation method thereof | |
| CN107759777A (en) | A kind of electroluminescent polymer and preparation method and application | |
| CN106279130A (en) | Luminescent material and preparation method thereof and the Organic Light Emitting Diode using this luminescent material | |
| CN107652221A (en) | A kind of derivative containing benzo carbazole structure and preparation method thereof and organic electroluminescence device | |
| CN103554444B (en) | A kind of white light polymer materials and preparation method thereof and application | |
| CN105418679A (en) | Triphenylphosphine oxide unit bridged bipolar host material and application thereof | |
| CN108250212A (en) | A kind of pyrrolizine derivaties and preparation method thereof and organic luminescent device | |
| CN104650154B (en) | Dark red smooth phosphorescent iridium complex and preparation method thereof and the organic electroluminescence device using the complex | |
| CN102850320B (en) | Compound containing dibenzothiophene sulfone 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 |