CN109651435A - A kind of bipolarity organic photoelectric functional material and preparation method - Google Patents
A kind of bipolarity organic photoelectric functional material and preparation method Download PDFInfo
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- CN109651435A CN109651435A CN201811567153.9A CN201811567153A CN109651435A CN 109651435 A CN109651435 A CN 109651435A CN 201811567153 A CN201811567153 A CN 201811567153A CN 109651435 A CN109651435 A CN 109651435A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 7
- 238000005401 electroluminescence Methods 0.000 claims description 6
- 150000002900 organolithium compounds Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- -1 tert-butyl dichloride phosphine Chemical compound 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052711 selenium Chemical group 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 239000008204 material by function Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 7
- 238000007740 vapor deposition Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 229920000144 PEDOT:PSS Polymers 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 230000005540 biological transmission Effects 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 3
- SPPLEVHTUMPNLQ-UHFFFAOYSA-N 10-[4-(4-carbazol-9-ylphenyl)sulfonylphenyl]-9,9-dimethylacridine Chemical compound C1=2C=CC=CC=2N(C2=C1C=CC=C2)C1=CC=C(S(=O)(=O)C2=CC=C(N3C4=CC=CC=C4C(C4=C3C=CC=C4)(C)C)C=C2)C=C1 SPPLEVHTUMPNLQ-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000007445 Chromatographic isolation Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000011097 chromatography purification Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- 238000004140 cleaning Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- FQHFBFXXYOQXMN-UHFFFAOYSA-M lithium;quinolin-8-olate Chemical compound [Li+].C1=CN=C2C([O-])=CC=CC2=C1 FQHFBFXXYOQXMN-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XSVXWCZFSFKRDO-UHFFFAOYSA-N triphenyl-(3-triphenylsilylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XSVXWCZFSFKRDO-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/64—Acridine or hydrogenated acridine ring systems
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- 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
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
- C07F9/65335—Six-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- 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
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6544—Six-membered rings
- C07F9/6547—Six-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract
The invention discloses a kind of bipolarity organic photoelectric functional materials, connect donor monomer by N-P=X resonant structure and obtain the bipolarity organic photoelectric functional material, structure is as shown in logical formula (I):Band gap of the present invention reaches 3.85eV, and triplet reaches 2.97eV, additionally photoelectric properties with higher, stability, film forming, dissolubility etc..The electroluminescent device external quantum efficiency with higher being prepared by the present invention, reaches 18.3%.
Description
Technical field
The present invention relates to organic photoelectrical material and preparation method, in particular to a kind of bipolarity organic photoelectric functional material and
Preparation method.
Background technique
Organic electroluminescent LED (Organic light-emitting diodes, OLEDs) is due to having driving electricity
Force down, the good characteristics such as luminous efficiency is high, visual angle is wide, operating temperature range is wide, illumination and in terms of have it is heavy
The application prospect wanted.For the carrier charge velocity and raising luminous efficiency of balanced light emitting device, usually in luminescent device
One layer of electron transfer layer being made of electron transport material and one layer of hole transmission layer being made of hole mobile material are introduced, but
The introducing of transport layer often results in the increase of luminescent device cost of manufacture, and in order to simplify the structure of luminescent device, exploitation has hole concurrently
The bipolar transmission material of conduction and electronic conductivity energy becomes research hotspot.Currently, the bipolar transmission material of building is mostly based on
Donor (Donor)-receptor (Acceptor) structure, the donor monomer and charge for introducing hole transport simultaneously in same molecule pass
Defeated receptor unit, to realize the bipolar transmission of hole and electronics.But such Donor-Acceptor structure, donor and by
Usually there is pi-conjugated effect between body unit, this will reduce the triplet and relatively narrow band gap of material.
Summary of the invention
Goal of the invention: it is an object of the present invention to provide a kind of bipolarity organic photoelectric functional material, which has wider band
The blue light material of gap and triplet with higher.
It is a further object of the present invention to provide the preparation methods of the bipolarity organic photoelectric functional material.
Technical solution: the present invention provides a kind of bipolarity organic photoelectric functional material, is connected by N-P=X resonant structure
Donor monomer obtains the bipolarity organic photoelectric functional material, and structure is as shown in logical formula (I):
Wherein, P is phosphorus atoms, and X is oxygen atom, sulphur atom or selenium atom, and R is any group in following group:
Wherein, N is nitrogen-atoms, O is oxygen atom, S is sulphur atom.
The bipolarity organic photoelectric functional material is the group for passing hole originally can be made to have by resonating to adjust
The ability of certain son that conducts electricity, assigns its excellent hole transport and electron transport ability, realizes the bipolar biography without acceptor groups
Defeated property, and the non-conjugated connection type of resonant structure ensure that material triplet with higher, it can be fine
Inhibition energy pass back to material of main part from guest materials.
Further, the structural formula of the bipolarity organic photoelectric functional material is following any:
The preparation method of the bipolarity organic photoelectric functional material, includes the following steps:
(1) under nitrogen protection, carbazole, phenoxazine, phenthazine or acridine are dissolved in tetrahydrofuran, after cooling, then dripped
Add n-BuLi to be reacted, forms organo-lithium compound system；
(2) under nitrogen protection, a tert-butyl dichloride phosphine is added into (1) described organo-lithium compound system, obtains
The derivative of the structure containing N-P；
(3) derivative for the structure containing N-P for obtaining (2) is dissolved in methylene chloride, and hydrogenperoxide steam generator is added and carries out
Oxidation reaction obtains solid through extraction, revolving, column excessively, that is, has the function of the bipolarity organic photoelectric material of N-P=O resonant structure
Material；The derivative for the N-P structure that (2) obtain is dissolved in methylene chloride, sulphur simple substance is added, carries out vulcanization reaction, extracted,
Revolving, excessively column obtain solid, i.e., with the bipolarity organic photoelectric functional material of N-P=S resonant structure；The N-P that (2) are obtained
The derivative of structure is dissolved in chloroform, and selenium powder is added, and carries out selenylation reaction, obtains solid through extraction, revolving, column excessively,
I.e. with the bipolarity organic photoelectric functional material of N-P=Se resonant structure.
Further, the molar ratio of carbazole, phenoxazine, phenthazine or acridine and n-BuLi is 1: 1 in the step (1)
~2.The molar ratio of a tert-butyl dichloride phosphine and the organo-lithium compound system is 0.5: 1 in the step (2).The step
Suddenly the mass concentration of hydrogenperoxide steam generator is 30% in (3).Hydrogen peroxide solution contains with described in step (3) peroxidization
The molar ratio of the derivative of N-P structure is 1~2: 1, reacts 4~12h at room temperature.Sulphur simple substance in step (3) vulcanization reaction
Molar ratio with the derivative of the structure containing N-P is 1~5: 1, reacts 4~12h at room temperature.Step (3) selenylation reaction
The molar ratio of middle selenium powder and the derivative of the structure containing N-P is 1~5: 1, reacts 4~12h at room temperature.
Further, the bipolarity organic photoelectric functional material is applied in organic electroluminescence device.
The utility model has the advantages that the present invention has wider band gap (3.85eV) and higher triplet (2.97eV), additionally
Photoelectric properties with higher, stability, film forming, dissolubility etc..Had by the electroluminescent device that the present invention is prepared
Higher external quantum efficiency, reaches 18.3%.
Detailed description of the invention
Fig. 1 is UV absorption (UV) spectrum and fluorescence hair of 1,2,3 product of embodiment under methylene chloride and filminess
Penetrate (PL) spectrum；
Fig. 2 be embodiment 1,2 products vapor deposition type electroluminescent device energy diagram；
Fig. 3 be embodiment 1,2 products vapor deposition type electroluminescent device Current density-voltage-brightness curve；
Fig. 4 is the vapor deposition type electroluminescent device efficiency chart of embodiment 1,2 products；
Fig. 5 be embodiment 1,2 products spin coating type electroluminescent device energy diagram；
Fig. 6 be embodiment 1,2 products spin coating type electroluminescent device Current density-voltage-brightness curve；
Fig. 7 is the spin coating type electroluminescent device efficiency chart of embodiment 1,2 products.
Specific embodiment
In the examples where no specific technique or condition is specified, according to the literature in the art described technology or conditions or
Person carries out according to product description.Reagents or instruments used without specified manufacturer, being can be by the normal of commercially available acquisition
Advise product.
Embodiment 1: the synthesis of photoelectric functional material 1 (t-BuPO)
Two mouthfuls of reaction flasks are taken, 1.0g carbazole is added, sealing vacuumizes, rouse argon gas repeatedly for three times, under the protection of nitrogen,
20mL anhydrous tetrahydro furan is added, is placed in -78 DEG C of dry ice/acetone batch cooling 10min.2.9mL is being measured just with syringe
The hexane solution of butyl lithium, is added dropwise in reaction flask, under nitrogen protection -78 DEG C of reaction 1h, and a tertiary fourth is then added
Base dichloride phosphine 0.62mL, then reacts at room temperature 8h.The water quenching reaction of reaction solution 10ml, with the methylene chloride of 3 × 30mL
Solution extraction, organic phase collection is simultaneously dry with anhydrous sodium sulfate, is concentrated to give crude product.Obtained crude product methylene chloride is molten
Solution, 30% hydrogenperoxide steam generator 0.4mL is added dropwise under 0 DEG C of ice bath, then reacts at room temperature 6h.The water of reaction solution 10mL
Quenching reaction is extracted with the dichloromethane solution of 3 × 30mL, and organic phase collection is simultaneously dry with anhydrous sodium sulfate, is concentrated to give thick production
Object obtains 1.88g white solid through column chromatographic isolation and purification.Yield: 72%.1H NMR(DMSO-d6, 400MHz) and δ (ppm):
8.18-8.16 (m, 4H), 7.60-7.57 (m, 4H), 7.29-7.26 (m, 8H), 1.60 (d, J=20Hz, 9H)13C NMR
(CDCl3,100MHz) δ (ppm): 141.11,141.08,126.61,126.48,126.42122.32,119.90,114.97,
39.89,38.85,26.43.HRMS (EI): m/z calcd for C28H25N2PO[M+Na]+: 459.1602；Found:
459.1601.Anal.calcd for C28H25N2PO:C 77.05, H 5.77, N 6.42；Found:C 77.07, H5.68, N
6.16。
Structure is as follows:
Embodiment 2: the synthesis of photoelectric functional material 2 (t-BuPS)
Two mouthfuls of reaction flasks are taken, 1.0g carbazole is added, sealing vacuumizes, rouse argon gas repeatedly for three times, under the protection of nitrogen,
20mL anhydrous tetrahydro furan is added, is placed in -78 DEG C of dry ice/acetone batch cooling 10min.2.9mL is being measured just with syringe
The hexane solution of butyl lithium, is added dropwise in reaction flask, under nitrogen protection -78 DEG C of reaction 1h, and a tertiary fourth is then added
Base dichloride phosphine 0.62mL, then reacts at room temperature 8h.The water quenching reaction of reaction solution 10ml, with the methylene chloride of 3 × 30mL
Solution extraction, organic phase collection is simultaneously dry with anhydrous sodium sulfate, is concentrated to give crude product.Obtained crude product methylene chloride is molten
Solution is added 0.29g sulphur simple substance, then reacts at room temperature 6h.The water quenching reaction of reaction solution 10mL, with the dichloromethane of 3 × 30mL
The extraction of alkane solution, organic phase collection is simultaneously dry with anhydrous sodium sulfate, is concentrated to give crude product, obtains through column chromatographic isolation and purification
1.43g white solid.Yield: 53%.1H NMR(DMSO-d6, 400MHz) δ (ppm): 8.18 (d, J=8Hz, 4H), 7.61 (d,
J=8Hz, 4H), 7.29-7.20 (m, 8H), 1.74 (d, J=20Hz, 9H)13C NMR(CDCl3, 100MHz) and δ (ppm):
141.10,141.07,126.85,126.79,126.22,122.34,119.77,115.78,46.06,45.31,
28.10.HRMS (EI): m/z calcd for C28H25N2PS[M+H]+: 453.1554；Found:
453.1548.Anal.calcd for C28H25N2PS:C 74.31, H5.57, N 6.19；Found:C 74.43H 5.54, N
5.94。
Structure is as follows:
Embodiment 3: the synthesis of photoelectric functional material 3 (t-BuPSe)
Two mouthfuls of reaction flasks are taken, 1.0g carbazole is added, sealing vacuumizes, rouse argon gas repeatedly for three times, under the protection of nitrogen,
20mL anhydrous tetrahydro furan is added, is placed in -78 DEG C of dry ice/acetone batch cooling 10min.2.9mL is being measured just with syringe
The hexane solution of butyl lithium, is added dropwise in reaction flask, under nitrogen protection -78 DEG C of reaction 1h, and a tertiary fourth is then added
Base dichloride phosphine 0.62mL, then reacts at room temperature 8h.The water quenching reaction of reaction solution 10ml, with the methylene chloride of 3 × 30mL
Solution extraction, organic phase collection is simultaneously dry with anhydrous sodium sulfate, is concentrated to give crude product.Obtained crude product methylene chloride is molten
Solution is added 0.71g selenium powder, then reacts at room temperature 6h.The water quenching reaction of reaction solution 10mL, with the methylene chloride of 3 × 30mL
Solution extraction, organic phase collection is simultaneously dry with anhydrous sodium sulfate, is concentrated to give crude product, obtains 1.43g through column chromatographic isolation and purification
White solid.Yield: 45%.1H NMR(DMSO-d6, 400MHz) and δ (ppm): 8.18 (d, J=8Hz, 4H), 7.63-7.61 (m,
4H), 7.29-7.20 (dt, J=36Hz, 8H), 1.78 (d, J=20Hz, 9H)13C NMR(CDCl3, 100MHz) and δ (ppm):
141.10,141.07,126.85,126.79,126.22,122.34,119.77,115.78,46.06,45.31,
28.10.Anal.calcd for C28H25N2PSe:C 67.33, H 5.05, N 5.61；Found:C 67.26, H 5.34, N
5.21。
Structure is as follows:
Embodiment 4: the performance test of vapor deposition type organic electroluminescence device
Device of the present invention using complex as luminescent layer can include: 1. conductive glass layers (ITO)；2. hole injection layer
PEDOT:PSS；3. hole transmission layer (TAPC)；4. exciton barrier-layer (mCP)；5. luminescent layer；6. electron transfer layer (TmPyPB)；
7. electron injecting layer (LiF)；8. cathode Al.The energy diagram of its vapor deposition type electroluminescent device is as shown in Figure 2.
The production method of vapor deposition type organic electroluminescence device are as follows: revolved in the glass substrate (ITO) through over cleaning first
PEDOT:PSS hole injection layer is applied, is then successively deposited.ITO/PEDOT:PSS (30nm)/1,3,5-Triazo-2,4,6-
Triphosphorine-2,2,4,4,6,6-tetrachloride (TAPC) (20nm)/N, N '-dicarbazo lyl-3,5-
Benzene (mCP) (8nm)/host:15wt%FIrpic (22nm)/1,3,5-tri (m-pyrid-3-yl-phenyl)
benzene(TmPyPB)(35nm)/LiF(1nm)/Al(100nm).Wherein Host is the material being prepared in above embodiments
1 (t-BuPO) or material 2 (t-BuPS).Current density-voltage-brightness curve of vapor deposition type electroluminescent device is as shown in Figure 3.
The efficiency curve of electroluminescent device provided by the invention is as shown in Figure 4.Test result is as shown in table 1:
1 experimental result of table
aData sequence is current efficiency, power efficiency, external quantum efficiency.
bIt is 100cd m that data sequence, which is brightness,-2, brightness is 1000cd m-2。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention should all
For equivalent substitute mode, it is included within the scope of the present invention.
Embodiment 5: the performance test of spin coating type organic electroluminescence device
Device of the present invention using complex as luminescent layer can include: 1. conductive glass layers (ITO)；2. hole injection layer
PEDOT:PSS；3. luminescent layer；4. exciton barrier-layer (DPEPO)；5. electron transfer layer (TmPyPB)；6. electron injecting layer
(Liq)；7. cathode Al.The energy diagram of its spin coating type electroluminescent device is as shown in Figure 5.
The production method of spin coating type organic electroluminescence device are as follows: revolved in the glass substrate (ITO) through over cleaning first
PEDOT:PSS hole injection layer and luminescent layer are applied, is then successively deposited.ITO/PEDOT:PSS (60nm)/host:20wt%10-
(4- ((4- (9H-carbazol-9-yl) phenyl) sulfonyl) phenyl) -9,9-dimethyl-9,10-
Dihydroacridine (CzAcSF): 15wt%FIr6 (40nm)/bis [2- (diphenylphosphino) phenyl]
ether oxide(DPEPO)(10nm)/TmPyPB(50nm)/8-hydroxyquinolinolato-lithium(Liq)
(1nm)/Al(100nm).Wherein Host is the material 1 (t-BuPO) or material 2 (t-BuPS) being prepared in above embodiments
It is blended with CzAcSF.Current density-voltage-brightness curve of spin coating type electroluminescent device is as shown in Figure 6.It is provided by the invention
The efficiency curve of electroluminescent device is as shown in Figure 7.Test result is as shown in table 2:
2 test result of table
aData sequence is current efficiency, power efficiency, external quantum efficiency.
bIt is 100cd m that data sequence, which is brightness,-2, brightness is 1000cd m-2。
Claims (10)
1. a kind of bipolarity organic photoelectric functional material, it is characterised in that: connect donor monomer by N-P=X resonant structure and obtain
To the bipolarity organic photoelectric functional material, structure is as shown in logical formula (I):
Wherein, P is phosphorus atoms, and X is oxygen atom, sulphur atom or selenium atom, and R is any group in following group:
Wherein, N is nitrogen-atoms, O is oxygen atom, S is sulphur atom.
2. bipolarity organic photoelectric functional material according to claim 1, it is characterised in that: the bipolarity organic photoelectric
The structural formula of functional material is following any:
3. the preparation method of bipolarity organic photoelectric functional material as described in claim 1, it is characterised in that: including walking as follows
It is rapid:
(1) under nitrogen protection, carbazole, phenoxazine, phenthazine or acridine are dissolved in tetrahydrofuran, after cooling, then are added dropwise just
Butyl lithium is reacted, and organo-lithium compound system is formed；
(2) under nitrogen protection, a tert-butyl dichloride phosphine is added into (1) described organo-lithium compound system, obtains containing N-P
The derivative of structure；
(3) derivative for the structure containing N-P for obtaining (2) is dissolved in methylene chloride, and hydrogenperoxide steam generator is added and is aoxidized
Reaction obtains solid through extraction, revolving, column excessively, i.e., with the bipolarity organic photoelectric functional material of N-P=O resonant structure；It will
(2) derivative of the N-P structure obtained is dissolved in methylene chloride, be added sulphur simple substance, carry out vulcanization reaction, through extraction, revolving,
It crosses column and obtains solid, i.e., with the bipolarity organic photoelectric functional material of N-P=S resonant structure；The N-P structure that (2) are obtained
Derivative be dissolved in chloroform, be added selenium powder, carry out selenylation reaction, through extraction, revolving, cross column obtain solid, that is, have
There is the bipolarity organic photoelectric functional material of N-P=Se resonant structure.
4. the preparation method of bipolarity organic photoelectric functional material according to claim 3, it is characterised in that: the step
(1) molar ratio of carbazole, phenoxazine, phenthazine or acridine and n-BuLi is 1: 1~2 in.
5. the preparation method of bipolarity organic photoelectric functional material according to claim 3, it is characterised in that: the step
(2) molar ratio of a tert-butyl dichloride phosphine and organo-lithium compound system is 0.5: 1 in.
6. the preparation method of bipolarity organic photoelectric functional material according to claim 3, it is characterised in that: the step
(3) mass concentration of hydrogenperoxide steam generator is 30% in.
7. the preparation method of bipolarity organic photoelectric functional material according to claim 3, it is characterised in that: the step
(3) 4~12h is reacted under oxidation reaction room temperature, wherein the molar ratio of the derivative of hydrogenperoxide steam generator and the structure containing N-P is 1~
2∶1。
8. the preparation method of bipolarity organic photoelectric functional material according to claim 3, it is characterised in that: the step
(3) vulcanization reaction reacts 4~12h at room temperature, wherein the molar ratio of the derivative of sulphur simple substance and the structure containing N-P is 1~5: 1.
9. the preparation method of bipolarity organic photoelectric functional material according to claim 3, it is characterised in that: the step
(3) selenylation reaction reacts 4~12h at room temperature, wherein the molar ratio of selenium powder and the derivative of the structure containing N-P is 1~5: 1.
10. the preparation method of bipolarity organic photoelectric functional material according to claim 1, it is characterised in that: described double
Polarity organic photoelectric functional material is applied in organic electroluminescence device.
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| CN112745351A (en) * | 2021-04-06 | 2021-05-04 | 南京邮电大学 | Preparation and application of novel hole transport material based on N-P = X resonance structure |
| CN117402188A (en) * | 2023-10-26 | 2024-01-16 | 南京邮电大学 | Organic long afterglow material based on diphenylacridine, preparation method and application thereof |
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