CN104292185A - Amino N-oxidation water/alcohol soluble oligomer, synthesis method and application thereof - Google Patents
Amino N-oxidation water/alcohol soluble oligomer, synthesis method and application thereof Download PDFInfo
- Publication number
- CN104292185A CN104292185A CN201410447250.XA CN201410447250A CN104292185A CN 104292185 A CN104292185 A CN 104292185A CN 201410447250 A CN201410447250 A CN 201410447250A CN 104292185 A CN104292185 A CN 104292185A
- Authority
- CN
- China
- Prior art keywords
- oligomer
- amido
- amino
- oxidizing water
- alcohol dissolubility
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/24—Oxygen atoms
-
- 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
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
-
- 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)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses an amino N-oxidation water/alcohol soluble oligomer, a synthesis method and application thereof. The synthesis method comprises the steps of: subjecting 2-bromofluorene, 4-(2-chloroethyl)morpholine hydrochloride and potassium hydroxide to heating reflux, conducting silica-gel column chromatography on a reaction crude product and then performing recrystallization in petroleum ether to obtain a bromofluorene monomer; reacting a both end brominated cyclic compound with alkyl bromide and 2-isopropyl-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborinane under the existence of a palladium catalyst to obtain a cyclic compound with boric acid ester at both ends; mixing the bromofluorene monomer and the cyclic compound with boric acid ester at both ends, carrying out reflux reaction under the protection of an inert gas, and performing cooling and purification to obtain an amino neutral oligomer; and oxidizing the N of a polar side chain in the amino neutral oligomer to obtain the amino N-oxidation water/alcohol soluble oligomer. The amino N-oxidation water/alcohol soluble oligomer can be applied to organic solar cell cathode surface modification materials and can achieve good electronic extraction and transmission performance.
Description
Technical field
The invention belongs to organic solar batteries field, be specifically related to a kind of novel amido N-oxidizing water/alcohol dissolubility oligomer and synthetic method thereof and application.
Background technology
Solar cell device is owing to having cheapness, the advantage such as clean, renewable and being widely used.Solar cell has the structure of sandwich, i.e. electrode and active layer.Between electrode and active layer, add interfacial layer, can make, between electrode and active layer, there is good ohmic contact, reduce the collection of contact resistance and the strong current carrier in pool.Having bibliographical information, by adding low official letter metal, metal oxide or salt as embellishing cathode interface material between active layer and negative electrode, can obtain the battery of superior performance, the metal even can contained by high merit, as cathode material, improves the stability of device.But these embellishing cathode interface materials need vacuum evaporation usually, increase the cost of manufacture of device, be unfavorable for preparing large-area flexible device.
Patent CN102898427 discloses a kind of water alcohol dissolubility pyridinium salt based on organic molecule, but its synthesis and device fabrication process complexity, packing factor and effciency of energy transfer etc. are lower.
Summary of the invention
The object of this invention is to provide a kind of amido N-oxidizing water/alcohol dissolubility oligomer, its Heat stability is good, synthetic method is comparatively simple, and the easier analysis and characterization of molecular structure, the difference between batch is little.
For achieving the above object, the technical scheme of employing is as follows:
A kind of amido N-oxidizing water/alcohol dissolubility oligomer, structure is:
In formula, R represents cyclics, and described cyclics is phenyl, fluorenyl, carbazyl, pyrryl or xenyl.
By such scheme, described amido N-oxidizing water/alcohol dissolubility oligomer has following structure:
By such scheme, described amido N-oxidizing water/alcohol dissolubility oligomer has following structure:
Wherein, R ' is C
1~ C
18alkyl.
By such scheme, described amido N-oxidizing water/alcohol dissolubility oligomer has following structure:
The preparation method of above-mentioned amido N-oxidizing water/alcohol dissolubility oligomer, comprises the following steps:
1) by 2-bromine fluorenes, 4-(2-chloroethyl) morpholine hydrochloride and potassium hydroxide reflux, reacting coarse product after silica gel column chromatography in sherwood oil recrystallization, obtain ethyl morpholine replace bromine fluorenes monomer;
2) cyclics of two ends bromo reacts with alkyl bromide, 2-sec.-propyl-4,4,5,5-tetramethyl--1,3,2-dioxaborinate under palladium catalyst, obtains the cyclics of two end band boric acid esters;
3) the bromine fluorenes monomer replaced by above-mentioned base morpholine and the cyclics of two end band boric acid esters are with the mixed in molar ratio of 2:1, and back flow reaction under protection of inert gas, cools, and obtain the neutral oligomer of amido after purification;
4) by the N oxidation of neutral for amido oligomer polar side chain, amido N-oxidizing water/alcohol dissolubility oligomer is obtained.
Above-mentioned amido N-oxidizing water/alcohol dissolubility oligomer is in the application of organic solar batteries cathode plane decorative material.
Beneficial effect of the present invention is:
Amido N-oxidizing water of the present invention/alcohol dissolubility oligomer can be dissolved in methyl alcohol, THF, DMSO and water polar solvent.
Amido N-oxidizing water of the present invention/alcohol dissolubility oligomer introduces interface-modifying layer, open circuit voltage and packing factor all increase, make device final energy efficiency of conversion reach 8.97% and 8.94% respectively, the solar cell device efficiency not adding interface-modifying layer is 6.86%
Amido N-oxidizing water of the present invention/alcohol dissolubility oligomer introduces interface-modifying layer, can effectively prevent electron-hole in the compound again of interface, and prolection layer film form is not by the erosion of cathode atoms simultaneously.
Accompanying drawing explanation
Fig. 1: embodiment 1,2 gained oligomer ultra-violet absorption spectrum in the solution (polymer concentration 1 × 10
-5m);
Fig. 2: the ultra-violet absorption spectrum of embodiment 1,2 gained oligomer filminess.
Embodiment
Following embodiment explains technical scheme of the present invention further, but not as limiting the scope of the invention.
The building-up process of amido N-oxidizing water of the present invention/alcohol dissolubility oligomer is as follows:
1) by 2-bromine fluorenes, 4-(2-chloroethyl) morpholine hydrochloride and potassium hydroxide reflux, reacting coarse product after silica gel column chromatography in sherwood oil recrystallization, obtain ethyl morpholine replace bromine fluorenes monomer;
2) cyclics of two ends bromo reacts with alkyl bromide, 2-sec.-propyl-4,4,5,5-tetramethyl--1,3,2-dioxaborinate under palladium catalyst, obtains the cyclics of two end band boric acid esters;
3) cyclics of the bromine fluorenes monomer replaced by above-mentioned ethyl morpholine and two end band boric acid esters is with the mixed in molar ratio of 2:1, and back flow reaction under protection of inert gas, cools, and obtains the neutral oligomer of amido after purification;
4) by the N oxidation of neutral for amido oligomer polar side chain, amido N-oxidizing water/alcohol dissolubility oligomer is obtained.
The amido N-oxidizing water/alcohol dissolubility oligomer of synthesis has following structure:
Gained amido N-oxidizing water/alcohol dissolubility oligomer can be applied in organic solar batteries cathode plane decorative material.It is dissolved in methyl alcohol, THF, DMSO and water polar solvent; Molecular structure is single, and molecular weight is determined, the difference between batch is less, and circulation ratio is higher; Inserted between solar cell organic active layer and metal electrode by the mode of spin coating and prove that it has good electronics extracting and transmission performance as cathode interface material.
Example 1
1) synthesis of bromo-9,9-bis-(2-ethyl morpholine) fluorenes (M1) of 2-:
By 2-bromine fluorenes (4.9g, 20mmol), 4-(2-chloroethyl) morpholine hydrochloride (9.3g, 50mmol) and potassium hydroxide (11.2g, 200mmol) be dissolved in 200mL tetrahydrofuran (THF), 80 DEG C of reaction 48h under the Ar environment of anhydrous and oxygen-free.By solvents tetrahydrofurane underpressure distillation after having reacted, first product purifies (silica gel, ethyl acetate: methyl alcohol=10:1 is eluent) with column chromatography, obtains Off-white solid recrystallization in sherwood oil, finally obtain white crystal 6.5g, productive rate is 69%.
2) synthesis of Isosorbide-5-Nitrae-two [9,9-bis-(2-ethyl morpholine) fluorenes] benzene (FNO-B-FNO-O):
By M1 (471mg in the there-necked flask of 50mL, 1mmol), 1.4-bis-boric acid (83mg, 0.5mmol), tetraphenyl phosphatization palladium (15mg, 0.01mmol), salt of wormwood (1.38g, 10mmol) join in the mixed solution of 10mL toluene 5mL water.Reaction system refluxes 48h under argon shield, is cooled to room temperature.First product purifies (silica gel, ethyl acetate: methyl alcohol: triethylamine=10:1:0.1 is eluent) with column chromatography, obtains faint yellow toner end 220mg, productive rate 51%.
Example 2
1) 1) synthesis of bromo-9,9-bis-(2-ethyl morpholine) fluorenes (M1) of 2-:
By 2-bromine fluorenes (4.9g, 20mmol), 4-(2-chloroethyl) morpholine hydrochloride (9.3g, 50mmol) and potassium hydroxide (11.2g, 200mmol) be dissolved in 200mL tetrahydrofuran (THF), 80 DEG C of reaction 48h under the Ar environment of anhydrous and oxygen-free.By solvents tetrahydrofurane underpressure distillation after having reacted, first product purifies (silica gel, ethyl acetate: methyl alcohol=10:1 is eluent) with column chromatography, obtains Off-white solid recrystallization in sherwood oil, finally obtain white crystal 6.5g, productive rate is 69%.
2) synthesis of 2,7-bis-bromo-9,9-dioctyl fluorene (M2)
By 2,7-dibromo fluorenes (5g, 15.5mmol), Tetrabutyl amonium bromide (0.1g, 0.31mmol), 200mL dimethyl sulfoxide (DMSO) is put in there-necked flask and forms suspension under violent stirring, instillation 50wt% aqueous sodium hydroxide solution 5mL, after reaction 1h, then drip 1-bromooctane (6.2g, 31mmol).Reaction mixture at room temperature stirs stopped reaction after 6h, and with ether (150mL × 3) extraction, organic phase saturated common salt is washed, and uses anhydrous magnesium sulfate drying.Solvent under reduced pressure distills, and product recrystallization in the mixed solvent of methanol/acetone obtains white, needle-shaped crystals 8g, productive rate 80%.
3) synthesis of 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-9,9-dioctyl fluorene (M3)
By M2 (5.4g, 10mmol) be dissolved in 60mL tetrahydrofuran (THF), at-78 DEG C, dropwise add the n-Butyl Lithium 15mL of 1.6mol/L, react 2h in a nitrogen atmosphere, and then add 2-sec.-propyl-4 fast, 4,5,5-tetramethyl--1,3,2-dioxaborinate 13mL, low-temp reaction 2h, slowly rise to room temperature reaction 24h.Reaction mixture is poured into water, and uses extracted with diethyl ether.Organic layer brine It also uses anhydrous magnesium sulfate drying.Faint yellow solid is obtained except after desolventizing, obtain white powdery solids with methyl alcohol/tetrahydrofuran (THF) recrystallization, and then purify (silica gel, ethyl acetate: normal hexane=1:15 is eluent) with column chromatography, obtain white, needle-shaped crystals 4.8g, productive rate 75%.
4) synthesis of FNO-F8-FNO-O
By M1 (471mg in the there-necked flask of 50mL, 1mmol), M3 (321mg, 0.5mmol) tetraphenyl phosphatization palladium (15mg, 0.01 mmol), salt of wormwood (1.38g, 10mmol) join in the mixed solution of 10mL toluene 5mL water.Reaction system refluxes 48h under argon shield, is cooled to room temperature.First product purifies (silica gel, ethyl acetate: methyl alcohol: triethylamine=10:1:0.1 is eluent) with column chromatography, obtains creamy white crystal 340mg, productive rate 58%.
The neutral oligomer obtained is dissolved in acetonitrile, adds peroxy acid metachloroperbenzoic acid (MCPBA) oxidation, react 48h under room temperature, because reaction conditions is very gentle, only have the N of polar side chain to be oxidized, obtain oxide compound FNO-F8-FNO-O.
The ultra-violet absorption spectrum of above-described embodiment 1,2 products therefrom is shown in accompanying drawing 1,2.
As shown in Figure 1, the absorption peak of embodiment 1,2 product FNO-B-FNO-O and FNO-F8-FNO-O in trichloromethane is respectively 327nm and 352nm, can find out that FNO-F8-FNO-O has obvious red shift relative to FNO-B-FNO-O.Illustrate to have stronger interaction between FNO-F8-FNO-O molecular chain, the conjugated structure that FNO-B-FNO-O is relatively weak simultaneously causes its relative FNO-F8-FNO-O blue shift.
As shown in Figure 2, embodiment 1,2 product FNO-B-FNO-O and FNO-F8-FNO-O is at solid film by spin coating chloroform soln on silica glass, and the absorption peak of its uv-visible absorption spectra lays respectively at 330nm and 359nm.The absorption of oligomer under solid film state can be found out relative to having red shift under solution state.This may be interact cause because the conjugated backbone of molecule under solid film state is more tending towards complanation and strong π-π.Their optical bandwidth can be calculated according to the sideband uv-absorbing of the film of oligomer.The optical bandwidth of FNO-B-FNO-O and FNO-F8-FNO-O is respectively 3.45eV and 3.11eV.
The prepare technical process of embodiment 1,2 product in organic solar batteries comprises: the preparation of organic active layer; The cleaning of ito glass and pre-treatment; The spin coating of hole transmission layer PEDOT:PSS; The spin coating of organic active layer; The spin coating of organic decoration layer; The evaporation of metal electrode.Prepare with PTB7 (poly [4,8-bis (2-ethylhexyloxyl) benzo [1,2-b:4,5-b'] dithiophen-e-2,6-diyl-alt-ethylh-exyl-3-fluorothithieno [3,4-b] thiophene-2-carboxylate-4,6-diyl] and PC
70bM ((6,6)-phenyl-C
70-butyric acid methylester) be the solar cell device of organic active layer.The structure of solar cell device is: ITO (tin indium oxide)/PEDOT:PSS/PTB7:PC
70bM/interlayer/Ca/Al.(wherein, interlayer represents FNO-B-FNO-O or FNO-F8-FNO-O)
Embodiment 1,2 is applied to solar cell at simulated solar irradiation AM1.5G (100mW/cm
2) irradiation under short-circuit current (J
sc), open circuit voltage (V
oc), packing factor (FF) and effciency of energy transfer (PCEs) parameter as shown in table 1.
Table 1
Do not add oligomer interface-modifying layer as can be seen from the table, only make the solar cell device efficiency of cathode material for 6.86% with Ca/Al, corresponding V
ocfor 0.71V, J
scfor 16.53mA/cm
2, FF is 59.After adding oligomer embellishing cathode interface layer FNO-B-FNO-O and FNO-F8-FNO-O, open circuit voltage and packing factor all increase, and make device final energy efficiency of conversion reach 8.97% and 8.94% respectively.The open circuit voltage V of solar cell
ocbe the important indicator affecting overall device performance, experimental result can find out the V of device
ocget a promotion after insertion interface-modifying layer comparatively large, be increased to 0.76V from 0.71V.By introducing interface-modifying layer FNO-B-FNO-O and FNO-F8-FNO-O, between interfacial layer and negative electrode, defining interface dipole thus reduce the work function of negative electrode, contributing to the transmission of electronics from organic active layer to negative electrode, and then improve the V of battery
ocand final energy transformation ratio.
Claims (6)
1. amido N-oxidizing water/alcohol dissolubility oligomer, is characterized in that structural formula is:
In formula, R represents cyclics, and described cyclics is phenyl, fluorenyl, carbazyl, pyrryl or xenyl.
2. amido N-oxidizing water/alcohol dissolubility oligomer as claimed in claim 1, is characterized in that having following structure:
3. amido N-oxidizing water/alcohol dissolubility oligomer as claimed in claim 1, is characterized in that having following structure:
Wherein, R ' is C
1~ C
18alkyl.
4. amido N-oxidizing water/alcohol dissolubility oligomer as claimed in claim 1, is characterized in that having following structure:
5. the preparation method of the amido N-oxidizing water described in any one of claim 1-4/alcohol dissolubility oligomer, is characterized in that comprising the following steps:
1) by 2-bromine fluorenes, 4-(2-chloroethyl) morpholine hydrochloride and potassium hydroxide reflux, reacting coarse product after silica gel column chromatography in sherwood oil recrystallization, obtain ethyl morpholine replace bromine fluorenes monomer;
2) cyclics of two ends bromo reacts with alkyl bromide, 2-sec.-propyl-4,4,5,5-tetramethyl--1,3,2-dioxaborinate under palladium catalyst, obtains the cyclics of two end band boric acid esters;
3) cyclics of the bromine fluorenes monomer replaced by above-mentioned ethyl morpholine and two end band boric acid esters is with the mixed in molar ratio of 2:1, and back flow reaction under protection of inert gas, cools, and obtains the neutral oligomer of amido after purification;
4) by the N oxidation of neutral for amido oligomer polar side chain, amido N-oxidizing water/alcohol dissolubility oligomer is obtained.
6. the amido N-oxidizing water described in any one of claim 1-4/alcohol dissolubility oligomer is in the application of organic solar batteries cathode plane decorative material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410447250.XA CN104292185B (en) | 2014-09-03 | 2014-09-03 | A kind of amido N-aoxidizes water/alcohol-soluble oligomer and synthetic method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410447250.XA CN104292185B (en) | 2014-09-03 | 2014-09-03 | A kind of amido N-aoxidizes water/alcohol-soluble oligomer and synthetic method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104292185A true CN104292185A (en) | 2015-01-21 |
| CN104292185B CN104292185B (en) | 2016-06-22 |
Family
ID=52312174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410447250.XA Expired - Fee Related CN104292185B (en) | 2014-09-03 | 2014-09-03 | A kind of amido N-aoxidizes water/alcohol-soluble oligomer and synthetic method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104292185B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004077014A2 (en) * | 2003-02-13 | 2004-09-10 | The Regents Of The University Of California | Methods and compositions for detection and analysis of polynucleotide-binding protein interactions using light harvesting multichromophores |
| CN101232078A (en) * | 2007-01-22 | 2008-07-30 | 铼德科技股份有限公司 | Organic solar battery and method for manufacturing the same |
| CN103319378A (en) * | 2013-06-27 | 2013-09-25 | 中国科学院宁波材料技术与工程研究所 | Zwitterionic organic small molecular solar cell cathode interface material, as well as preparation method and use thereof |
| CN103396321A (en) * | 2013-06-27 | 2013-11-20 | 中国科学院宁波材料技术与工程研究所 | Alcohol-soluble conjugate organic micromolecular material for cathode interface of solar cell, and preparation method and purpose thereof |
-
2014
- 2014-09-03 CN CN201410447250.XA patent/CN104292185B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004077014A2 (en) * | 2003-02-13 | 2004-09-10 | The Regents Of The University Of California | Methods and compositions for detection and analysis of polynucleotide-binding protein interactions using light harvesting multichromophores |
| CN101232078A (en) * | 2007-01-22 | 2008-07-30 | 铼德科技股份有限公司 | Organic solar battery and method for manufacturing the same |
| CN103319378A (en) * | 2013-06-27 | 2013-09-25 | 中国科学院宁波材料技术与工程研究所 | Zwitterionic organic small molecular solar cell cathode interface material, as well as preparation method and use thereof |
| CN103396321A (en) * | 2013-06-27 | 2013-11-20 | 中国科学院宁波材料技术与工程研究所 | Alcohol-soluble conjugate organic micromolecular material for cathode interface of solar cell, and preparation method and purpose thereof |
Non-Patent Citations (1)
| Title |
|---|
| MAO LI ET AL.: "Electrochemical-Coupling Layer-by-Layer (ECC-LbL) Assembly", 《J. AM. CHEM. SOC.》, vol. 133, 22 April 2011 (2011-04-22), pages 7348 - 7351, XP055213569, DOI: doi:10.1021/ja202768k * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104292185B (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106467547B (en) | A kind of non-fullerene solar cell acceptor material based on multi-fused rings class and its preparation method and application | |
| JP5425338B2 (en) | Copolymer containing anthracene and pearselenol, its production method and its application | |
| CN104177378A (en) | Tetra-substituted perylene diimide dimer, preparation method of tetra-substituted perylene diimide dimer and use of tetra-substituted perylene diimide dimer in organic photovoltaic device | |
| CN103435782B (en) | Organic semiconducting materials containing 9,9 '-difluorenylene and derivant thereof and preparation method thereof and application | |
| CN108586496A (en) | Zigzag type middle width strip gap small molecule electron donor materials based on the different chromene of thieno and its application | |
| CN105315273A (en) | Polyceptor-structure small molecule compound and preparing method and application thereof | |
| CN106084186A (en) | One class solar cell interface based on indenofluorene derivant material | |
| CN112280008B (en) | Bridged asymmetric benzodiazole and/or pyridine diazole birceptor polymer semiconductor and preparation method and application thereof | |
| CN109517142B (en) | Star-shaped D-A structure conjugated molecule based on tri-indeno five-membered aromatic heterocycle, and preparation method and application thereof | |
| CN108192083B (en) | Conjugated polymer containing trifluoromethyl as well as preparation method and application thereof | |
| CN102827355A (en) | Benzodifuran-based polymer materials and their photovoltaic application | |
| CN110964040B (en) | Benzoxadiazole-based acceptor material and preparation method and application thereof | |
| CN105418899B (en) | A kind of preparation method and applications for organic semi-conductor conjugated polymer | |
| CN104250364B (en) | A kind of amphion amido polyfluorene derivative and its synthetic method and application | |
| CN111138454B (en) | Hole transport material based on indeno [1,2-b ] carbazole and preparation method and application thereof | |
| CN106832231A (en) | Containing 1,2,3 triazol iso-indoles 5,7（2H, 6H）The conjugated polymer and its preparation method of diketone and application | |
| Fan et al. | Synthesis and photovoltaic properties of two star-shaped molecules involving phenylquinoxaline as core and triphenylamine and thiophene units as arms | |
| CN103865044A (en) | Copolymer containing cyclopentadithiophene and benzodi(benzoselenadiazole), and preparation method and application thereof | |
| CN104292185A (en) | Amino N-oxidation water/alcohol soluble oligomer, synthesis method and application thereof | |
| CN103724283B (en) | 2,7-alkyl replaces phenanthro-[9,10-b] pyrazine derivative monomer and preparation method thereof and polymer | |
| CN107304218B (en) | Ortho-bridged perylene diimide dimer, preparation method thereof and application thereof in organic photovoltaic device | |
| CN105399930B (en) | One kind is used for organic semi-conductor conjugated polymer and preparation method thereof | |
| CN109912631A (en) | It is respectively to the Uniformpoly thiophene derivative and preparation method thereof by electronic unit with benzene thiophene and pyrydinothiadiazole | |
| CN104230849B (en) | A kind of oligomer based on fluorenes and synthetic method thereof and application | |
| CN110790772A (en) | Hydroxyquinoline-based metal organic micromolecule complex material grafted with perylene diimide and aromatic group and preparation 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160622 Termination date: 20190903 |