CN105153085A - Derivative of dibenzofuran and preparation method and application thereof - Google Patents

Derivative of dibenzofuran and preparation method and application thereof Download PDF

Info

Publication number
CN105153085A
CN105153085A CN201510599795.7A CN201510599795A CN105153085A CN 105153085 A CN105153085 A CN 105153085A CN 201510599795 A CN201510599795 A CN 201510599795A CN 105153085 A CN105153085 A CN 105153085A
Authority
CN
China
Prior art keywords
precursor
oxide
diphenylene
palladium catalyst
derivative
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
Application number
CN201510599795.7A
Other languages
Chinese (zh)
Other versions
CN105153085B (en
Inventor
任辉彩
庞茂印
杨福山
田绍振
史汝金
胡葆华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Valiant Co Ltd
Original Assignee
Valiant Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Valiant Co Ltd filed Critical Valiant Co Ltd
Priority to CN201510599795.7A priority Critical patent/CN105153085B/en
Publication of CN105153085A publication Critical patent/CN105153085A/en
Application granted granted Critical
Publication of CN105153085B publication Critical patent/CN105153085B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to a derivative of dibenzofuran and a preparation method and application thereof. The preparation method of the derivative of the dibenzofuran comprises the steps that carbon-nitrogen coupling is performed on p-bromoanisole and p-methoxyaniline to obtain a first precursor; a two-step reaction is performed on the first precursor and 4,4'-dibromodiphenylamine protected by butyloxycarbonyl to obtain a second precursor, and a two-step reaction is performed on the first precursor and 3,6-dibromocarbazole protected by butyloxycarbonyl to obtain a third precursor; carbon-nitrogen coupling is performed on all the precursors and 2,8-dibromodibenzofuran under the action of a palladium catalyst to obtain the derivative of the dibenzofuran. The prepared derivative of the dibenzofuran is easy to synthesize, low in cost, high in glass transition temperature and good in heat stability, is a hole-transport material with the good properties and has the good effect when the derivative is applied to perovskite solar cells.

Description

Derivative of a kind of diphenylene-oxide and its preparation method and application
Technical field
The present invention relates to derivative of a kind of diphenylene-oxide and its preparation method and application, area of solar cell.
Background technology
In recent years, a kind of brand-new solar cell based on organic/inorganic composite perofskite material, due to advantages such as its high efficiency of conversion, the equal simple preparation technology of liquid/gas and extremely low tooling costs, causes the great attention of international academic community.At present, uhligite solar cell has become one of study hotspot important in current photovoltaic art (electronic component and material, 2014,33 (8)).
In the device architecture of uhligite solar cell, hole mobile material is important integral part, and it plays the effect of transporting holes.Originally, uhligite sun power uses liquid electrolyte, but liquid electrolyte is easily revealed, encapsulation difficulty; And calcium titanium ore bed is easily by electrochemical dissolution, stability test is caused to reduce, the lost of life.Solid-state organic hole transport material is adopted to replace liquid electrolyte to efficiently solve this problem.At present, the high-level efficiency uhligite solar cell of bibliographical information uses more hole mobile material to be Spiro-OMeTAD (Phys.Chem.Chem.Phys.2012,14,779-789; Appl.Phys.Lett.2012,100,173512-173514; Adv.EnergyMater.2011, Isosorbide-5-Nitrae 07 – 414), but its synthesis price is very high, is more than five times of the price of gold, in the cost of battery, occupies larger proportion.Researcher is also constantly attempting novel organic hole transport material (Angew.Chem.Int.Ed.2014,53,4085-4088; Adv.EnergyMater.2014,1401185; Phys.Chem.Chem.Phys., 2015,17,5991-5998), comprise organic micromolecule compound and polymer materials.But organic micromolecule compound second-order transition temperature is lower, and material is crystallization very easily, cause device unstable, repeatability is poor; Polymer materials molecular weight is uncertain, is difficult to realize suitability for industrialized production.
Summary of the invention
For above technical problem, the diphenylene-oxide that present inventor is cheap replaces expensive spiral shell fluorenes core, introduces diaryl-amine or the carbazole group with excellent hole transport performance in its 2,8-position.The diaryl-amine introduced or carbazole group are dendritic, molecule can be made to have space three-dimensional structure on the one hand, avoid material crystalline; Greatly can improve the thermostability of material on the other hand, and then improve battery efficiency.
Technical problem to be solved by this invention is to provide derivative of a kind of diphenylene-oxide and its preparation method and application, and preparation technology is simple, with low cost, obtains the material with excellent hole transport performance.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of derivative of diphenylene-oxide, has the one in having structure:
The present invention also provides a kind of preparation method of derivative of diphenylene-oxide, comprising:
1) synthesis of precursor 1: by the 1.0:1.1:1.2 mixing in molar ratio of para-bromoanisole, P-nethoxyaniline and potassium tert.-butoxide, obtain mixture I, toluene is added in mixture I, mixing, under nitrogen protection, add palladium catalyst and Phosphine ligands, the mol ratio of palladium catalyst, Phosphine ligands, para-bromoanisole is 0.005:0.01:1,110 DEG C are reacted 5 hours, obtain precursor 1;
2) synthesis of precursor 2: by 4,4'-dibromo pentanoic and (BOC) 2o (tert-Butyl dicarbonate) 1:1 mixing in molar ratio, obtain mixture II, in mixture II, add tetrahydrofuran (THF) (THF), mixing, then add DMAP (DMAP), mix, the mol ratio of described DMAP and 4,4'-dibromo pentanoic is 0.1:1, under nitrogen protection, 65 DEG C of reaction 2h, obtain intermediate 1; By intermediate 1 and precursor 1 in molar ratio 1:2.2 mix, obtain mixture III, toluene is added in mixture III, mixing, under nitrogen protection, adds organic bases, palladium catalyst and Phosphine ligands, the mol ratio of organic bases, palladium catalyst, Phosphine ligands and intermediate 1 is 2.5:0.005:0.01:1,110 DEG C of reaction 4h, recrystallization, obtains intermediate 2; Add methylene dichloride dissolving in intermediate 2 after, add trifluoroacetic acid, under nitrogen protection, 20-25 DEG C is stirred 10 minutes, and recrystallization, obtains precursor 2;
3) synthesis of precursor 3: by 3,6-dibromo carbazole and (BOC) 2o 1:1 mixing in molar ratio, obtain mixture IV, in mixture IV, add THF, mixing, then add DMAP, mix, the mol ratio of described DMAP and 3,6-dibromo carbazole is 0.1:1, and under nitrogen protection, 65 DEG C of reaction 2h, obtain intermediate 3; By intermediate 3 and precursor 1 in molar ratio 1:2.2 mix, obtain mixture V, toluene is added in mixture V, mixing, under nitrogen protection, adds organic bases, palladium catalyst and Phosphine ligands, organic bases, palladium catalyst, Phosphine ligands and middle 3 mol ratio be 2.5:0.04:0.08:1,110 DEG C are reacted 3 hours, and recrystallization, obtains intermediate 4; Add methylene dichloride dissolving in intermediate 4 after, add trifluoroacetic acid, under nitrogen protection, 20-25 DEG C is stirred 10 minutes, and recrystallization, obtains precursor 3;
4) by precursor 1 and 2, the 2.2:1 mixing in molar ratio of 8-dibromo diphenylene-oxide, obtain mixture VI, in mixture VI, add toluene, mix, organic bases, palladium catalyst and Phosphine ligands is added under nitrogen protection, the mol ratio of organic bases, palladium catalyst, Phosphine ligands and 2,8-dibromo diphenylene-oxide is 2.5:0.02:0.04:1.0, is heated to 80 DEG C of reactions 8 hours, recrystallization, obtains the derivative BF-001 of diphenylene-oxide;
5) by precursor 2 and 2,8-dibromo diphenylene-oxide is in molar ratio (2.2 ~ 2.5): 1 mixing, obtain mixture VII, toluene is added in mixture VII, mix, organic bases, palladium catalyst and Phosphine ligands is added under nitrogen protection, organic bases, palladium catalyst, Phosphine ligands and 2, the mol ratio of 8-dibromo diphenylene-oxide is 2.5:(0.02 ~ 0.04): (0.04 ~ 0.08): 1.0, be heated to 110 DEG C of reactions 9 hours, recrystallization, obtains the derivative BF-002 of diphenylene-oxide;
6) by precursor 3 and 2; 8-dibromo diphenylene-oxide is in molar ratio (2.2 ~ 2.5): 1 mixing; obtain mixture VIII; toluene is added in mixture VIII; mix; organic bases, palladium catalyst and Phosphine ligands is added under nitrogen protection; organic bases, palladium catalyst, Phosphine ligands and 2; the mol ratio of 8-dibromo diphenylene-oxide is 2.5:(0.02 ~ 0.04): (0.04 ~ 0.08): 1.0. is heated to 110 DEG C of reactions 20 hours; recrystallization, obtains the derivative BF-003 of diphenylene-oxide.
On the basis of technique scheme, the present invention can also do following improvement.
Further, 2), 3), 4), 5) and 6) in, the solvent of described recrystallization is one or both in normal hexane, toluene, ethyl acetate.
Further, 1), 2), 3), 4), 5) and 6) in, described palladium catalyst is Pd 2dba 3(three (two Bian fork acetone) two palladiums), palladium, Pd (dppf) Cl 2one in (1,1'-bis-(diphenyl phosphine) ferrocene palladium chloride (II)); Described Phosphine ligands is the one in tri-butyl phosphine, tri-butyl phosphine a tetrafluoro borate, DPEphos (two (2-diphenylphosphine) phenylate);
Further, 2), 3), 4), 5) and 6) in, described organic bases is potassium tert.-butoxide or sodium tert-butoxide.
The present invention also provides a kind of application of derivative in uhligite solar cell device of above-mentioned diphenylene-oxide.
The present invention also provides a kind of uhligite solar cell device, comprising: FTO glass substrate, fine and close TiO 2layer, porous TiO 2layer, calcium titanium ore bed, hole transmission layer and Ag electrode, described hole transmission layer adopts the derivative of above-mentioned diphenylene-oxide to make.
The present invention also provides a kind of preparation method of uhligite solar cell device, comprise: first cleaning, dry and with on the FTO glass substrate of ultraviolet-ozone process, by the butanol solution spin-coating film three times of two (acetylacetone based) di-isopropyl titanic acid ester of 0.15-0.3mol/L, after each spin coating, FTO glass substrate is at 125 DEG C of dry 5min, after third time drying, FTO glass substrate, at 500 DEG C of calcination 15min, forms fine and close TiO 2layer, then spin coating TiO 2the ethanolic soln of slurry, TiO 2the mass ratio of slurry and ethanol (ethanol used is straight alcohol) is 4:7,500 DEG C of calcination 30min, forms porous TiO 2layer, then FTO glass substrate is proceeded in glove box, spin coating 10.3mol/LPbI 2dMF solution, 90 DEG C dry 15min, finally the FTO glass substrate of above-mentioned oven dry is immersed in 6mg/mLCH 3nH 320-30s in the aqueous isopropanol of I, after Virahol drip washing, dry 10min for 70 DEG C, after cooling, the chlorobenzene solution of the derivative of spin coating 72.3mg/mL diphenylene-oxide, proceeds to vacuum evaporation room evaporation Ag electrode, obtained uhligite solar cell device.
Raw material of the present invention all can commercially available or conventionally synthesize.
Beneficial effect of the present invention:
1) electrochemical results of compound of the present invention shows, its HUMO energy level, between-5.20 ~-5.25eV, well can mate with the energy level (-5.43eV) of calcium titanium ore bed;
2) compound of the present invention is owing to having dendritic structure, better heat stability, and second-order transition temperature is higher, can form good amorphous membrance, is conducive to the stable of battery properties.Its thermodynamic property is as shown in the table:
The thermodynamic property of table 1 compound
Compound BF-001 BF-002 BF-003
Tg/℃ 105 130 135
Tm/℃ 223 292.5 298
Td/℃ 301 412 430
Wherein, Tg represents second-order transition temperature, and Tm represents fusing point, and Td represents decomposition temperature.
3) compound preparation technology of the present invention is simple, and raw material is easy to get, cheap, and very suitability for industrialized is produced.
4) compound of the present invention is higher in the photoelectric transformation efficiency of uhligite solar cell device, illustrates that compound of the present invention is the hole mobile material of a class excellent property.
Accompanying drawing explanation
Fig. 1 is the structure iron of the uhligite solar cell device that compound of the present invention is made as hole mobile material, and wherein, the parts representated by each label are as follows:
1, glass substrate, 2, FTO negative electrode, 3, TiO 2electron transfer layer, 4, calcium titanium ore bed, 5, hole transmission layer, 6, Ag electrode;
Fig. 2 is the current density voltage curve figure of the uhligite solar cell be made up as hole mobile material of compd B F-002 of the present invention;
Fig. 3 is the current density voltage curve figure of the uhligite solar cell be made up as hole mobile material of compd B F-003 of the present invention.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
The preparation of embodiment one precursor 1
Reaction scheme is as follows:
149.6g (0.8mol) para-bromoanisole is added successively in 2L there-necked flask, 108.3g (0.88mol) P-nethoxyaniline and 107.5g (1.2mol) potassium tert.-butoxide, obtain mixture I, in mixture I, add 800g toluene, logical N 2after displacement 10min, then drop into 0.9g (0.004mol) palladium, 1.62g (0.008mol) tri-butyl phosphine, 110 DEG C of back flow reaction 5 hours.The cancellation that adds water is reacted, separatory, extraction, and solvent is sloughed in decompression, obtains crude product.Crude product, through toluene and ethyl acetate mixed solvent (mass ratio 3:1) recrystallization, obtains 119g light yellow solid, yield 64.9%.GC-MS:C 14h 15nO 2: calculated value: 229.11, measured value [M] +=229.27.
The preparation of embodiment two precursor 2
Reaction scheme is as follows:
The synthesis of intermediate 1:
Be in 500mL there-necked flask, add 20g (0.06mol) 4,4'-dibromo pentanoic and 13.1g (0.06mol) (BOC) to volume 2o, mixes, and obtains mixture II, adds 100gTHF (tetrahydrofuran (THF)), nitrogen protection in said mixture II.0.75g (0.006mol) DMAP (DMAP) is added, 65 DEG C of reaction 2h in system.Reaction is finished, and is cooled to 20-25 DEG C, removal of solvent under reduced pressure, obtains brown oil, and silicagel column filters, and obtains 51.6g white solid, yield 98%.LC-MS:C 17h 17br 2nO 2, calculated value: 424.96, measured value: [M+2] +=427.13.
The synthesis of intermediate 2:
In 2L there-necked flask, add 42.7g (0.1mol) intermediate 1,50.4g (0.22mol) precursor 1 (being prepared by embodiment one), obtain mixture III.800g toluene is added, logical nitrogen protection in mixture III.Then 28.0g (0.25mol) potassium tert.-butoxide is added, 0.46g (5.0 × 10 -4mol) Pd 2(dba) 3, 0.20g (0.001mol) tri-butyl phosphine, 110 DEG C of back flow reaction 4h.Reaction is finished, and system is cooled to 20-25 DEG C, suction filtration, removal of solvent under reduced pressure, normal hexane recrystallization, obtains 61.6g white solid, yield: 85%.LC-MS:C 45h 45n 3o 6, calculated value: 723.86, measured value: [M+H] +=724.35.
The synthesis of precursor 2:
Add 12.3g (0.017mol) intermediate 2,60g methylene dichloride in 250mL there-necked flask, open and stir.49.2gTFA (trifluoroacetic acid) is added until completely dissolved, 20-25 DEG C of reaction 10min in system.Reaction is finished, and removal of solvent under reduced pressure, obtains black solid.Re crystallization from toluene, obtains 8.48g white solid.Yield 80%.LC-MS:C 40h 37n 3o 4: calculated value: 623.74, measured value [M+H] +=624.47.
The preparation of embodiment three precursor 3
Reaction scheme is as follows:
The synthesis of intermediate 3:
Feed intake when preparation technology with the synthesis of intermediate 1.Obtain white solid 15.1g, yield 95%.LC-MS:C 17h 12brNO 2, calculated value: 422.95, measured value: [M+2] +=425.11.
The synthesis of intermediate 4:
In 100mL there-necked flask, add 2.4g (0.01mol) intermediate 3,5.0g (0.022mol) precursor 1 (being prepared by embodiment one), obtain mixture V.50g toluene is added, logical nitrogen protection in mixture V.Then 2.4g (0.025mol) sodium tert-butoxide is added, 0.29g (4 × 10 -4mol) Pd (dppf) Cl 2, 0.24g (8 × 10 -4mol) tri-butyl phosphine a tetrafluoro borate, mixes, and opens mechanical stirring, 110 DEG C of reaction 3h.Reaction is finished, and system is cooled to 20-25 DEG C, suction filtration, removal of solvent under reduced pressure, re-crystallizing in ethyl acetate, obtains 6.0g white solid, yield: 84.7%.LC-MS:C 45h 43n 3o 6, calculated value: 721.32, measured value: [M+H] +=722.34.
The synthesis of precursor 3:
The preparation process of precursor 3 is with the synthesis of precursor 2, and crude product, through toluene and normal hexane recrystallization (mass ratio 4:1), obtains 12.0g white solid.Yield 83%.LC-MS:C 40h 35n 3o 4: calculated value: 621.26, measured value [M+H] +=622.42.
The preparation of embodiment four BF-001
Reaction scheme is as follows:
In 250mL there-necked flask, add 5.04g (0.022mol) precursor 1 (being prepared by embodiment one) and 3.26g (0.01mol) 2,8-dibromo diphenylene-oxide, obtain mixture VI, in mixture VI, add 40g toluene.Open and stir, system is that light red is muddy, N 2displacement system 10min.2.8g (0.025mol) potassium tert.-butoxide is added, 0.18g (2 × 10 in system -4mol) Pd 2(dba) 3with 0.12g (4 × 10 -4mol) tri-butyl phosphine a tetrafluoro borate, 80 DEG C are reacted 8 hours.Reaction is finished, and is cooled to 20-25 DEG C, and by reaction solution suction filtration, the direct silicagel column of filtrate filters, toluene drip washing, and decompression desolventizing, obtains red-brown oily matter 6.5g.In above-mentioned crude product, add toluene and normal hexane recrystallization (mass ratio 2:1), vacuum drying oven dries 3h, obtains pale yellow powder 2.5g, yield: 40.2%. 1h-NMR (500MHz, d6-DMSO) δ/ppm:7.60 (d, 2H), 7.54 (s, 1H), 7.52 (s, 1H), 7.05 (d, 1H), 7.04 (d, 1H), 6.90 ~ 6.88 (m, 8H), 6.85 ~ 6.83 (m, 8H), 3.7 (s, 12H) .LC-MS:C 40h 34n 2o 5; Calculated value: 622.25, measured value [M+H] +=623.32.mp:220～222℃。
The preparation of embodiment five BF-002
Reaction scheme is as follows:
Realize respectively by following three kinds of schemes:
Scheme one: add 8.8g (0.014mol) precursor 2 (being prepared by embodiment two) and 2.1g (6.4 × 10 in 250mL there-necked flask -3mol) 2,8-dibromo diphenylene-oxide, add 100g toluene.Open and stir, system is that light red is muddy, N 2displacement system 10min.1.8g (0.016mol) sodium tert-butoxide is added, 0.12g (1.28 × 10 in system -4mol) Pd 2(dba) 3with 0.14g (2.56 × 10 -4mol) DPEphos, 110 DEG C are reacted 9 hours.Reaction is finished, and is cooled to 20-25 DEG C, and by reaction solution suction filtration, the direct silicagel column of filtrate filters, toluene drip washing, and decompression desolventizing, obtains red-brown spumescence crude product.Normal hexane and re-crystallizing in ethyl acetate (mass ratio 1:3), obtain pale yellow powder 5.0g, yield: 55%.LC-MS:C 92h 78n 6o 9; Calculated value: 1411.64; Measured value: [M] +=1411.52.
Scheme two: add 9.98g (0.016mol) precursor 2 (being prepared by embodiment two) and 2.1g (6.4 × 10 in 250mL there-necked flask -3mol) 2,8-dibromo diphenylene-oxide, add 100g toluene.Open and stir, system is that light red is muddy, N 2displacement system 10min.1.8g (0.016mol) potassium tert.-butoxide is added, 0.24g (2.6 × 10 in system -4mol) Pd 2(dba) 3with 0.10g (5.12 × 10 -4mol) tri-butyl phosphine, 110 DEG C are reacted 9 hours.Reaction is finished, and is cooled to 20-25 DEG C, and by reaction solution suction filtration, the direct silicagel column of filtrate filters, toluene drip washing, and decompression desolventizing, obtains red-brown spumescence crude product.Normal hexane and re-crystallizing in ethyl acetate (mass ratio 1:3), obtain pale yellow powder 5.3g, yield: 58%.LC-MS:C 92h 78n 6o 9; Calculated value: 1411.64; Measured value: [M] +=1411.52.
Scheme three: add 9.2g (0.015mol) precursor 2 (being prepared by embodiment two) and 2.1g (6.4 × 10 in 250mL there-necked flask -3mol) 2,8-dibromo diphenylene-oxide, add 100g toluene.Open and stir, system is that light red is muddy, N 2displacement system 10min.1.8g (0.016mol) potassium tert.-butoxide is added, 0.17g (1.92 × 10 in system -4mol) Pd 2(dba) 3with 0.1g (3.84 × 10 -4mol) tri-butyl phosphine a tetrafluoro borate, 110 DEG C are reacted 9 hours.Reaction is finished, and is cooled to 20-25 DEG C, and by reaction solution suction filtration, the direct silicagel column of filtrate filters, toluene drip washing, and decompression desolventizing, obtains red-brown spumescence crude product.Normal hexane and re-crystallizing in ethyl acetate (mass ratio 1:3), obtain pale yellow powder 5.1g, yield: 56%.LC-MS:C 92h 78n 6o 9; Calculated value: 1411.64; Measured value: [M] +=1411.52.
The preparation of embodiment six BF-003
Reaction scheme is as follows:
Realize respectively by following three kinds of schemes:
Scheme one: add 2.1g (3.38 × 10 in 250mL there-necked flask -3mol) precursor 3 (being prepared by embodiment three) and 0.5g (1.53 × 10 -3mol) 2,8-dibromo diphenylene-oxide, add 100g toluene.Open and stir, system is that light red is muddy, N 2displacement system 10min.0.43g (3.84 × 10 is added in system -3mol) potassium tert.-butoxide, 0.007g (3.07 × 10 -5mol) Pd (OAc) 2with 0.018g (6.2 × 10 -5mol) tri-butyl phosphine a tetrafluoro borate, 110 DEG C are reacted 20 hours.Reaction is finished, and is cooled to 20-25 DEG C, and by reaction solution suction filtration, the direct silicagel column of filtrate filters, toluene drip washing, and decompression desolventizing, obtains light brown red spumescence crude product.Crude product, through toluene and re-crystallizing in ethyl acetate (mass ratio 4:1), obtains pale yellow powder shape product 1.2g, yield: 55.5%. 1h-NMR (500MHz, d6-DMSO) δ/ppm:8.56 (s, 2H), 8.01 (d, 2H), 7.76 (m, 6H), 7.28 (d, 4H), 7.08 (m, 6H), 6.81 ~ 6.86 (m, 34H), 3.68 (s, 24H) LC-MS:C 92h 78n 6o 9; Calculated value: 1407.61; Measured value: [M] +=1407.58.
Scheme two: add 2.36g (3.8 × 10 in 250mL there-necked flask -3mol) precursor 3 (being prepared by embodiment three) and 0.5g (1.53 × 10 -3mol) 2,8-dibromo diphenylene-oxide, add 100g toluene.Open and stir, system is that light red is muddy, N 2displacement system 10min.0.37g (3.84 × 10 is added in system -3mol) sodium tert-butoxide, 0.045g (6.14 × 10 -5mol) Pd (dppf) Cl 2with 0.025g (1.24 × 10 -4mol) tri-butyl phosphine, 110 DEG C are reacted 20 hours.Reaction is finished, and is cooled to 20-25 DEG C, and by reaction solution suction filtration, the direct silicagel column of filtrate filters, toluene drip washing, and decompression desolventizing, obtains light brown red spumescence crude product.In above-mentioned crude product, add normal hexane and re crystallization from toluene (mass ratio 4:1), obtain pale yellow powder shape product 1.7g, yield: 65%. 1h-NMR (500MHz, d6-DMSO) δ/ppm:8.56 (s, 2H), 8.01 (d, 2H), 7.76 (m, 6H), 7.28 (d, 4H), 7.08 (m, 6H), 6.81 ~ 6.86 (m, 34H), 3.68 (s, 24H) LC-MS:C 92h 78n 6o 9; Calculated value: 1407.61; Measured value: [M] +=1407.58.
Scheme three: add 2.2g (3.52 × 10 in 250mL there-necked flask -3mol) precursor 3 (being prepared by embodiment three) and 0.5g (1.53 × 10 -3mol) 2,8-dibromo diphenylene-oxide, add 100g toluene.Open and stir, system is that light red is muddy, N 2displacement system 10min.0.43g (3.84 × 10 is added in system -3mol) potassium tert.-butoxide, 0.042g (4.6 × 10 -5mol) Pd 2(dba) 3with 0.027g (9.3 × 10 -5mol) tri-butyl phosphine a tetrafluoro borate, 110 DEG C are reacted 20 hours.Reaction is finished, and is cooled to 20-25 DEG C, and by reaction solution suction filtration, the direct silicagel column of filtrate filters, toluene drip washing, and decompression desolventizing, obtains light brown red spumescence crude product.In above-mentioned crude product, add normal hexane and re-crystallizing in ethyl acetate (mass ratio 4:1), obtain pale yellow powder shape product 1.4g, yield: 64.8%. 1h-NMR (500MHz, d6-DMSO) δ/ppm:8.56 (s, 2H), 8.01 (d, 2H), 7.76 (m, 6H), 7.28 (d, 4H), 7.08 (m, 6H), 6.81 ~ 6.86 (m, 34H), 3.68 (s, 24H) LC-MS:C 92h 78n 6o 9; Calculated value: 1407.61; Measured value: [M] +=1407.58.
The uhligite solar cell device of embodiment seven compound
Fig. 1 shows the uhligite solar cell device prepared as hole transmission layer by compound of the present invention (BF-001, BF-002, BF-003), comprising: FTO glass substrate, fine and close TiO 2layer, porous TiO 2layer, calcium titanium ore bed 4, hole transmission layer 5 and Ag electrode 6, wherein, FTO glass substrate is made up of glass substrate 1 and FTO negative electrode 2 (fluorine-doped tin oxide glass electrode), fine and close TiO 2layer and porous TiO 2layer is as TiO 2electron transfer layer 3, calcium titanium ore bed 4 is as light-absorption layer.
The production process of described uhligite solar cell device:
1) clean: first with the surface of washing composition cleaning FTO glass substrate, then with ethanol and acetone ultrasonic remove organic pollutant, then use ultrapure water three times, clean FTO glass substrate nitrogen dries up, again with ultraviolet-ozone process 25min, ensure surface clean, clean;
2) fine and close TiO is prepared 2layer: the butanol solution of two for 0.15mol/L (acetylacetone based) di-isopropyl titanic acid ester is spin-coated on clean FTO glass substrate, 125 DEG C of dry 5min; The butanol solution of two for 0.3mol/L (acetylacetone based) di-isopropyl titanic acid ester is spin-coated on clean FTO glass substrate, 125 DEG C of dry 5min; Again the butanol solution of two for 0.3mol/L (acetylacetone based) di-isopropyl titanic acid ester is spin-coated on clean FTO glass substrate, 125 DEG C of dry 5min; 500 DEG C of calcination 15min, form fine and close TiO 2layer;
3) porous TiO is prepared 2layer: spin coating TiO 2the suspension liquid that slurry and ethanol (4:7, m/m, ethanol used is straight alcohol) are made into, then 500 DEG C of calcination 30min, form porous TiO 2layer;
4) calcium titanium ore bed is prepared: proceed in glove box by FTO glass substrate, spin coating 10.3mol/LPbI 2the solution of/DMF, then dries 15min for 90 DEG C; Substrate is immersed in CH 3nH 3solution (the CH of I/ Virahol 3nH 3the concentration of I is 6mg/mL) middle 20-30s, then uses Virahol drip washing, cools, obtained calcium titanium ore bed after 70 DEG C of oven dry 10min.
5) hole transmission layer is prepared: the derivatives concentration of preparation diphenylene-oxide is the chlorobenzene solution of 72.3mg/mL, add three kinds of additives: the acetonitrile solution, the 28.8 μ L4-tert .-butylpyridine that are respectively 29 μ L520mg/mLLi-TFSI (two (trifluoromethane sulfonic acid acyl) imine lithium), 24 μ L300mg/mL tri-(2-(1H pyrazol-1-yl) pyridine) close the acetonitrile solution of cobalt, stirring at normal temperature 1h.Then configured solution is spun to step 4) calcium titanium ore bed on.
6) vacuum evaporation room is placed in, vacuum evaporation metal A g, obtained uhligite solar cell device.
BF-003 prepared by the BF-002 prepared for embodiment five and embodiment six is described as the hole transmission layer of above-mentioned solar cell device (uhligite solar cell), and the structure of described uhligite solar cell device is: FTO glass substrate/fine and close TiO 2layer/porous TiO 2layer/CH 3nH 3pbI 3(uhligite) layer/hole transmission layer/Ag electrode, using the BF-002 of example five preparation as the hole transmission layer of uhligite solar cell, the current density voltage curve of this device is as shown in Figure 2; Using the BF-003 of example six preparation as the hole transmission layer of uhligite solar cell, the current density voltage curve of this device as shown in Figure 3.The units test data prepared for hole transmission layer with BF-002 and BF-003 are respectively as shown in table 2:
The device data of table 2 compound
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (7)

1. a derivative for diphenylene-oxide, is characterized in that, has the one in having structure:
2. a preparation method for the derivative of diphenylene-oxide, is characterized in that, comprising:
1) synthesis of precursor 1: by the 1.0:1.1:1.2 mixing in molar ratio of para-bromoanisole, P-nethoxyaniline and potassium tert.-butoxide, obtain mixture I, toluene is added in mixture I, mixing, under nitrogen protection, add palladium catalyst and Phosphine ligands, the mol ratio of palladium catalyst, Phosphine ligands, para-bromoanisole is 0.005:0.01:1,110 DEG C are reacted 5 hours, obtain precursor 1;
2) synthesis of precursor 2: by 4,4'-dibromo pentanoic and tert-Butyl dicarbonate in molar ratio 1:1 mix, and obtain mixture II, in mixture II, add tetrahydrofuran (THF), mixing, add DMAP again, mix, described DMAP and 4, the mol ratio of 4'-dibromo pentanoic is 0.1:1, under nitrogen protection, 65 DEG C of reaction 2h, obtain intermediate 1; By intermediate 1 and precursor 1 in molar ratio 1:2.2 mix, obtain mixture III, toluene is added in mixture III, mixing, under nitrogen protection, adds organic bases, palladium catalyst and Phosphine ligands, the mol ratio of organic bases, palladium catalyst, Phosphine ligands and intermediate 1 is 2.5:0.005:0.01:1,110 DEG C of reaction 4h, recrystallization, obtains intermediate 2; Add methylene dichloride dissolving in intermediate 2 after, add trifluoroacetic acid, under nitrogen protection, 20-25 DEG C is stirred 10 minutes, and recrystallization, obtains precursor 2;
3) synthesis of precursor 3: by 3,6-dibromo carbazole and (BOC) 2o 1:1 mixing in molar ratio, obtain mixture IV, in mixture IV, add THF, mixing, then add DMAP, mix, the mol ratio of described DMAP and 3,6-dibromo carbazole is 0.1:1, and under nitrogen protection, 65 DEG C of reaction 2h, obtain intermediate 3; By intermediate 3 and precursor 1 in molar ratio 1:2.2 mix, obtain mixture V, toluene is added in mixture V, mixing, under nitrogen protection, adds organic bases, palladium catalyst and Phosphine ligands, organic bases, palladium catalyst, Phosphine ligands and middle 3 mol ratio be 2.5:0.04:0.08:1,110 DEG C are reacted 3 hours, and recrystallization, obtains intermediate 4; Add methylene dichloride dissolving in intermediate 4 after, add trifluoroacetic acid, under nitrogen protection, 20-25 DEG C is stirred 10 minutes, and recrystallization, obtains precursor 3;
4) by precursor 1 and 2, the 2.2:1 mixing in molar ratio of 8-dibromo diphenylene-oxide, obtain mixture VI, in mixture VI, add toluene, mix, organic bases, palladium catalyst and Phosphine ligands is added under nitrogen protection, the mol ratio of organic bases, palladium catalyst, Phosphine ligands and 2,8-dibromo diphenylene-oxide is 2.5:0.02:0.04:1.0, is heated to 80 DEG C of reactions 8 hours, recrystallization, obtains the derivative BF-001 of diphenylene-oxide;
5) by precursor 2 and 2,8-dibromo diphenylene-oxide is in molar ratio (2.2 ~ 2.5): 1 mixing, obtain mixture VII, toluene is added in mixture VII, mix, organic bases, palladium catalyst and Phosphine ligands is added under nitrogen protection, organic bases, palladium catalyst, Phosphine ligands and 2, the mol ratio of 8-dibromo diphenylene-oxide is 2.5:(0.02 ~ 0.04): (0.04 ~ 0.08): 1.0, be heated to 110 DEG C of reactions 9 hours, recrystallization, obtains the derivative BF-002 of diphenylene-oxide;
6) by precursor 3 and 2; 8-dibromo diphenylene-oxide is in molar ratio (2.2 ~ 2.5): 1 mixing; obtain mixture VIII; toluene is added in mixture VIII; mix; organic bases, palladium catalyst and Phosphine ligands is added under nitrogen protection; organic bases, palladium catalyst, Phosphine ligands and 2; the mol ratio of 8-dibromo diphenylene-oxide is 2.5:(0.02 ~ 0.04): (0.04 ~ 0.08): 1.0. is heated to 110 DEG C of reactions 20 hours; recrystallization, obtains the derivative BF-003 of diphenylene-oxide.
3. preparation method according to claim 2, is characterized in that, 2), 3), 4), 5) and 6) in, the solvent of described recrystallization is one or both in normal hexane, toluene, ethyl acetate.
4. the preparation method according to Claims 2 or 3, is characterized in that, 1), 2), 3), 4), 5) and 6) in, described palladium catalyst is Pd 2dba 3, palladium, Pd (dppf) Cl 2in one; Described Phosphine ligands is the one in tri-butyl phosphine, tri-butyl phosphine a tetrafluoro borate, DPEphos;
2), 3), 4), 5) and 6) in, described organic bases is potassium tert.-butoxide or sodium tert-butoxide.
5. the application of derivative in uhligite solar cell device of a diphenylene-oxide as claimed in claim 1.
6. a uhligite solar cell device, is characterized in that, comprising: FTO glass substrate, fine and close TiO 2layer, porous TiO 2layer, calcium titanium ore bed, hole transmission layer and Ag electrode, described hole transmission layer adopts the derivative of diphenylene-oxide according to claim 1 to make.
7. the preparation method of a uhligite solar cell device, it is characterized in that, comprise: first cleaning, dry and with on the FTO glass substrate of ultraviolet-ozone process, by the butanol solution spin-coating film three times of two (acetylacetone based) di-isopropyl titanic acid ester of 0.15-0.3mol/L, after each spin coating, FTO glass substrate at 125 DEG C of dry 5min, third time drying after, FTO glass substrate, at 500 DEG C of calcination 15min, forms fine and close TiO 2layer, then spin coating TiO 2the ethanolic soln of slurry, TiO 2the mass ratio of slurry and ethanol is 4:7,500 DEG C of calcination 30min, forms porous TiO 2layer, then FTO glass substrate is proceeded in glove box, spin coating 10.3mol/LPbI 2dMF solution, 90 DEG C dry 15min, finally the FTO glass substrate of above-mentioned oven dry is immersed in 6mg/mLCH 3nH 320-30s in the aqueous isopropanol of I, after Virahol drip washing, dry 10min for 70 DEG C, after cooling, the chlorobenzene solution of the derivative of spin coating 72.3mg/mL diphenylene-oxide, proceeds to vacuum evaporation room evaporation Ag electrode, obtained uhligite solar cell device.
CN201510599795.7A 2015-09-18 2015-09-18 Derivative of dibenzofuran and preparation method and application thereof Active CN105153085B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510599795.7A CN105153085B (en) 2015-09-18 2015-09-18 Derivative of dibenzofuran and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510599795.7A CN105153085B (en) 2015-09-18 2015-09-18 Derivative of dibenzofuran and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN105153085A true CN105153085A (en) 2015-12-16
CN105153085B CN105153085B (en) 2017-05-03

Family

ID=54794179

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510599795.7A Active CN105153085B (en) 2015-09-18 2015-09-18 Derivative of dibenzofuran and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN105153085B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107311975A (en) * 2017-06-15 2017-11-03 中节能万润股份有限公司 A kind of derivative of dibenzothiophenes and its application
US9890240B2 (en) 2016-05-25 2018-02-13 International Business Machines Corporation Ladder polybenzodifurans
CN108148074A (en) * 2018-01-09 2018-06-12 中节能万润股份有限公司 A kind of dithieno cyclopentanone compound and its preparation method and application
EP3410506A4 (en) * 2016-01-25 2018-12-26 Ricoh Company, Ltd. Photoelectric conversion element
CN110128399A (en) * 2019-05-31 2019-08-16 常州大学 Based on five yuan of heteroaromatic organic molecule materials of dibenzo and its synthetic method and as the application of hole transmission layer
CN111747938A (en) * 2020-07-03 2020-10-09 长春海谱润斯科技有限公司 Arylamine compound and organic electroluminescent device thereof
CN113262816A (en) * 2021-05-28 2021-08-17 中钢集团南京新材料研究院有限公司 Catalytic system and method for synthesizing benzo [1,2-b:4,5-b ] dibenzofuran by using same
CN113956457A (en) * 2021-11-16 2022-01-21 丹阳市精通眼镜技术创新服务中心有限公司 PC-based blue-light-proof resin and preparation method thereof
CN114315883A (en) * 2022-01-17 2022-04-12 万华化学集团股份有限公司 Dibenzofuran phenol IVB group metal complex, preparation method thereof, catalyst system and olefin polymerization method
CN117003672A (en) * 2023-08-09 2023-11-07 湖南正量工程技术有限公司 Preparation method of BOC-4,4' -dinitrodiphenylamine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102850334A (en) * 2012-08-28 2013-01-02 李崇 Derivative compound treating dibenzofuran as core framework, and its application in OLED (organic light emission diode)
WO2013042460A1 (en) * 2011-09-20 2013-03-28 コニカミノルタホールディングス株式会社 Organic electroluminescent element, lighting device and display device
US20150131302A1 (en) * 2013-11-13 2015-05-14 Semiconductor Energy Laboratory Co., Ltd. Organic Compound, Light-Emitting Element, Display Module, Lighting Module, Light-Emitting Device, Display Device, Electronic Device, and Lighting Device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013042460A1 (en) * 2011-09-20 2013-03-28 コニカミノルタホールディングス株式会社 Organic electroluminescent element, lighting device and display device
CN102850334A (en) * 2012-08-28 2013-01-02 李崇 Derivative compound treating dibenzofuran as core framework, and its application in OLED (organic light emission diode)
US20150131302A1 (en) * 2013-11-13 2015-05-14 Semiconductor Energy Laboratory Co., Ltd. Organic Compound, Light-Emitting Element, Display Module, Lighting Module, Light-Emitting Device, Display Device, Electronic Device, and Lighting Device

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3410506A4 (en) * 2016-01-25 2018-12-26 Ricoh Company, Ltd. Photoelectric conversion element
US10435505B2 (en) 2016-05-25 2019-10-08 International Business Machines Corporation Ladder polybenzodifurans
US9890240B2 (en) 2016-05-25 2018-02-13 International Business Machines Corporation Ladder polybenzodifurans
US9944747B2 (en) 2016-05-25 2018-04-17 International Business Machines Corporation Ladder polybenzodifurans
CN107311975A (en) * 2017-06-15 2017-11-03 中节能万润股份有限公司 A kind of derivative of dibenzothiophenes and its application
CN108148074A (en) * 2018-01-09 2018-06-12 中节能万润股份有限公司 A kind of dithieno cyclopentanone compound and its preparation method and application
CN110128399A (en) * 2019-05-31 2019-08-16 常州大学 Based on five yuan of heteroaromatic organic molecule materials of dibenzo and its synthetic method and as the application of hole transmission layer
CN110128399B (en) * 2019-05-31 2021-11-23 常州大学 Organic molecular material based on dibenzo five-membered aromatic heterocycle, synthetic method thereof and application of organic molecular material as hole transport layer
CN111747938A (en) * 2020-07-03 2020-10-09 长春海谱润斯科技有限公司 Arylamine compound and organic electroluminescent device thereof
CN113262816A (en) * 2021-05-28 2021-08-17 中钢集团南京新材料研究院有限公司 Catalytic system and method for synthesizing benzo [1,2-b:4,5-b ] dibenzofuran by using same
CN113956457A (en) * 2021-11-16 2022-01-21 丹阳市精通眼镜技术创新服务中心有限公司 PC-based blue-light-proof resin and preparation method thereof
CN114315883A (en) * 2022-01-17 2022-04-12 万华化学集团股份有限公司 Dibenzofuran phenol IVB group metal complex, preparation method thereof, catalyst system and olefin polymerization method
CN114315883B (en) * 2022-01-17 2023-10-20 万华化学集团股份有限公司 Dibenzofuran phenol IVB metal complex and preparation method thereof, catalyst system and olefin polymerization method
CN117003672A (en) * 2023-08-09 2023-11-07 湖南正量工程技术有限公司 Preparation method of BOC-4,4' -dinitrodiphenylamine
CN117003672B (en) * 2023-08-09 2024-05-28 湖南正量工程技术有限公司 Preparation method of BOC-4,4' -dinitrodiphenylamine

Also Published As

Publication number Publication date
CN105153085B (en) 2017-05-03

Similar Documents

Publication Publication Date Title
CN105153085A (en) Derivative of dibenzofuran and preparation method and application thereof
CN106977491B (en) Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof
CN104844464B (en) A kind of 9,9 '-Spirobifluorene dendrimer and preparation method and application
CN105622442A (en) Tert-butyl spirobifluorene compound and preparation method and application thereof
KR102385317B1 (en) Three component copolymers for semiconductor, Preparation method thereof and Organic semiconductor device comprising the same
EP3648187B1 (en) Perovskite solar cell
CN105198792A (en) Carbazole diarylamine dendritic compound as well as preparation method and application of carbazole diarylamine dendritic compound
CN112979611B (en) Bowl alkenyl perovskite solar cell hole transport layer material and preparation method and application thereof
CN103288848A (en) Benzo terthiophene compound as well as preparation method and usage thereof
CN112707882A (en) Spiro [ fluorene-9, 9' -xanthene ] nuclear hole transport material and preparation method and application thereof
CN110606856A (en) 3-alkyl thiophene-based hepta-fused heterocyclic conjugated small molecule and preparation method and application thereof
KR20150002216A (en) Isoindigo derivative based compounds, methods for manufacturing the same, and soluble-processed organic photovolatic devices comprising the same
CN107805254B (en) Porphyrin micromolecular perovskite cathode buffer layer material and preparation method and application thereof
KR101484007B1 (en) new organic semiconductor compound and a method for manufacturing the same
Kula et al. 9, 9′-bifluorenylidene derivatives as novel hole-transporting materials for potential photovoltaic applications
CN107311975A (en) A kind of derivative of dibenzothiophenes and its application
CN103304568A (en) Tripolyindole compound, and preparation method and use thereof
Zhang et al. Benzotrithiophene-based sp2 carbon-conjugated microporous polymers for green light-triggered oxidation of amines to imines
Chang et al. Step-efficient access to new starburst hole-transport materials with carbazole end-groups for perovskite solar cells via direct C–H/C–Br coupling reactions
CN110152739B (en) Porous organic compound of in-situ supported palladium nanoparticles, synthetic method and application
CN110600612B (en) P-i-n type perovskite battery hole transport layer based on self-assembly engineering
Zhu et al. Asymmetrical planar acridine-based hole-transporting materials for highly efficient perovskite solar cells
CN114133385B (en) Hole transport material with carbazole as core and thiophene or phenoxazine as end group, and synthesis method and application thereof
CN113788832B (en) chrysene -base aza-bis [6] helicene compound and application thereof in hole transport material and solar cell
CN113336772B (en) Hole transport material and synthesis method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A derivative of dibenzofuran and its preparation method and Application

Effective date of registration: 20211202

Granted publication date: 20170503

Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd.

Pledgor: VALIANT Co.,Ltd.

Registration number: Y2021980013807

PC01 Cancellation of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20220823

Granted publication date: 20170503

Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd.

Pledgor: VALIANT Co.,Ltd.

Registration number: Y2021980013807