CN105061730A - Fluorine-containing phenanthrene quinoxaline and thiophene conjugated polymer - Google Patents

Fluorine-containing phenanthrene quinoxaline and thiophene conjugated polymer Download PDF

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CN105061730A
CN105061730A CN201510449945.6A CN201510449945A CN105061730A CN 105061730 A CN105061730 A CN 105061730A CN 201510449945 A CN201510449945 A CN 201510449945A CN 105061730 A CN105061730 A CN 105061730A
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polymer
quinoxaline
fluorine
thiophene
containing phenanthrene
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CN105061730B (en
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高潮
武海梅
边庆真
赵宝锋
王维平
安忠维
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Xian Modern Chemistry Research Institute
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Abstract

The invention discloses a fluorine-containing phenanthrene quinoxaline and thiophene conjugated polymer, the energy gap and the HOMO energy level of the polymer are reduced simultaneously, and needs of polymer photovoltaic cell photoactivity layer electron donor materials is met. The conjugated polymer has the structural general formula shown in the description. The polymer disclosed by the invention has deeper HOMO energy level than a polymer D and can be as deep as -5.67 eV, and high open circuit voltage of more than 0.89 V can be obtained when the polymer is applied in photovoltaic cells.

Description

Fluorine-containing phenanthrene is for the conjugated polymers of quinoxaline and thiophene
Technical field
The invention belongs to filed of functional, be specifically related to the conjugated polymers of a kind of fluorine-containing phenanthrene for quinoxaline and thiophene.
Background technology
Polymer photovoltaic cell is a kind of photovoltaic device converted solar energy into electrical energy, and due to low cost, the manufacturing processed simple and light weight outstanding advantages such as to be easy to carry is subject to the favor of scientific research personnel.It is the current key technical problem being badly in need of solving in this field that the photoelectric transformation efficiency how improving battery makes it to commercially produce.By the core that the active coating forming to body and acceptor material is device, in view of current acceptor material multiselect be fullerene derivate (PCBM) when, therefore develop high-efficiency polymer donor material most important to raising cell photoelectric efficiency of conversion.
Polymkeric substance is as the chief component of device photoactive layer, and its absorption spectrum affects the short-circuit current of battery, and the difference of lowest unoccupied molecular orbital (LUMO) energy level of highest occupied molecular orbital (HOMO) energy level and PCBM determines the open circuit voltage of device.Therefore, desirable polymer materials should have wider absorption namely containing narrower optical energy gap, is conducive to the short-circuit current of boost device; There is lower HOMO energy level simultaneously, ensure that device can obtain larger open circuit voltage.One alternately will form D-A type conjugated polymer backbone to electric unit (D) and short of electricity unit (A), realize by intermolecular interaction the important channel method that material energy level and energy gap regulate being become to the efficient donor polymer of exploitation at present.
Quinoxaline molecule draws electrically stronger nitrogen-atoms because itself having two, has obtained good result in the devices, in recent years enjoy the concern of scientific research personnel as a class novel short of electricity unit application in polymkeric substance.Such as material FTQ (JournalofMaterialsChemistryC.2013,1,630-637), this polymkeric substance is formed by quinoxaline and thiophene copolymerization.Its absorption bands is positioned at 300-730nm, and absorb the strongest with 360nm and 622nm place, ABSORPTION EDGE is 730nm, and corresponding optical energy gap is 1.70eV; Oxidizing potential is 0.79V, and corresponding HOMO energy level is-5.51eV.The polymer battery best photoelectric conversion efficiency of this material and the blended preparation of PCBM is 5.27%, and wherein open circuit voltage is 0.87V, and short-circuit current is 10.11mA/cm 2.
Although above-mentioned materials has achieved good opto-electronic conversion result, but due to quinoxaline unit contained in such polymer molecular structure, they are 2 years old, 3 are all substituted by phenyl, consequent sterically hindered effect makes two phenyl ring and quinoxaline molecular backbone chain structure form certain torsion, can not be coexisted same plane, polymer molecule conjugated degree is caused to reduce, optical energy gap can not absorb sunlight more greatly effectively, produce comparatively multi-photon and carry out opto-electronic conversion, performance is that the short-circuit current of battery is less than normal in the devices, become the important bottleneck hindering device photoelectric efficiency of conversion to promote.
Summary of the invention
For the deficiencies in the prior art, the present invention develops a kind of based on the D-A type donor polymer material of fluorine-containing phenanthrene for quinoxaline-thiophene-structure, material property is optimized, the final object realizing lifting photovoltaic device photoelectric transformation efficiency by the molecular structure improving modified polymer.
To achieve these goals, the technical solution used in the present invention is as follows: utilize phenanthrenequione structural compounds to substitute quinoxaline unit 2, the substituting group phenyl ring of 3, containing 5 aromatic nucleus in the polymer molecule skeleton that program design obtains, thus the coplanar structure that composition one is complete, have higher conjugated degree compared with the molecule replaced with phenyl, the absorption spectrum can widening polymkeric substance further produces narrower optical energy gap, and performance in the devices can the short-circuit current of effective boost device.In addition, in polymer backbone conformation, retain the fluorine atom drawing electronic capability stronger equally, reduce the HOMO energy level of polymkeric substance, ensure that device has higher open circuit voltage.
Specifically, a kind of fluorine-containing phenanthrene of the present invention is for the conjugated polymers of quinoxaline and thiophene, and its general structure is such as formula shown in I:
In formula, R 1, R 2can identical also can be different,
Work as R 1during=H, R 2alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20.
Work as R 2during=H, R 1alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20.
Work as R 1=R 2time, be alkyl or the alkoxyl group of the straight or branched of 4 to 20.
The present invention has following technical characterstic:
Work as R 2during for hydrogen atom, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in II:
Work as R 1during for hydrogen atom, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in III:
When R1 and R2 is octyloxy, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in IV:
Fluorine-containing phenanthrene disclosed by the invention, for the conjugated polymers of quinoxaline and thiophene, carries out according to reaction mechanism as follows:
Concrete synthesis step is as follows:
(1) fluorine-containing phenanthrene is for the preparation of quinoxaline and derivative thereof
By 5 fluorine-containing 4,7-bis-bromo-2,1,3-diazosulfide is dissolved in dehydrated alcohol, adds sodium borohydride at 0 DEG C in batches, then reacts 20h under room temperature, reaction terminates rear distillation under vacuum and removes ethanol, adds suitable quantity of water, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying, crude product obtains fluorinated diamine through silica column purification, then with 2,3-dialkyl group/alkoxyl group phenanthrenequione take acetic acid as solvent reaction, obtained 11 fluorine-containing 10,13-bis-bromo-2,3-dialkyl group/alkoxyl group quinoxalines.
(2) fluorine-containing phenanthrene is for the preparation of the D-A type conjugated polymers of quinoxaline and thiophene
This reaction is carried out under nitrogen protection, by short of electricity unit 11 fluorine-containing 10, 13-bis-bromo-2, the molar weight of 3-dialkyl group/alkoxyl group quinoxaline is as matching criterion, with 2 of equimolar amount, 5-bis-(tin trimethyl) thiophene, join in two mouthfuls of dry flasks, toluene dissolves, fluorine-containing phenanthrene controls at about 0.03mol/L for quinoxaline monomer concentration, catalyzer three (dibenzylideneacetone) two palladium of 0.02 times of molar weight and the part tri-o-tolyl phosphorus of 0.08 times of molar weight is added after ventilation 0.5h, continue ventilation 0.5h, then heating is started, after back flow reaction 24h, stopped reaction, system is cooled to room temperature, reaction solution is instilled sedimentation in methyl alcohol, filter, the polymkeric substance collected is 50 DEG C of baking 12h in vacuum drying oven, use methyl alcohol successively, normal hexane, chloroform carries out surname extraction, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filter, obtain such as formula the conjugated polymers of the fluorine-containing phenanthrene shown in I for quinoxaline and thiophene.
Beneficial effect:
(1) the present invention has wider absorption spectrum, and compared with polymkeric substance D, absorption spectrum there occurs obvious red shift, significantly reduces the optical energy gap of polymkeric substance;
(2) the present invention has the HOMO energy level darker than polymkeric substance D, can be deep to-5.67eV, be applied in photovoltaic cell the high open circuit voltage obtaining >0.89V;
(3) the present invention possesses the feature of thin pillar and dark HOMO energy level, very useful to the photovoltaic performance improving photovoltaic device.
Accompanying drawing explanation
Fig. 1 is the abosrption spectrogram of polymer A, D.
Fig. 2 is the C-V figure of polymer A, D.
Fig. 3 is the I-V figure of polymer device A, D.
Embodiment
Below in conjunction with drawings and Examples, particular content of the present invention is described in more detail.
Below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Embodiment 1: the synthesis of intermediate
(1) preparation of fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (compound 1) of 4-
Fluoro-4,7-bis-bromo-2,1, the 3-diazosulfides (5g, 0.016mol) of 5-are dissolved in 150ml dehydrated alcohol, add NaBH4 (11.1g, 0.29mol) in batches, then react 20h under room temperature at 0 DEG C.After reaction terminates, remove ethanol, add 160ml water, extraction into ethyl acetate, saturated common salt water washing organic phase with distillation under vacuum, last anhydrous MgSO4 is dry.Concentrated removal organic solvent, the thick product n-hexane/ethyl acetate obtained (volume ratio is 25:1) silica gel column chromatography, obtains fluoro-3,6-bis-bromo-1, the 2-phenylenediamine 3.5g of 4-, productive rate 78%.
The preparation of (2) 1,2-bis-(3-octyloxyphenyl) second diketone (compound 2)
To CuBr (4.33g, in THF solution 30.2mmol), (40ml) adds LiBr (5.25g, 60.4mmol), stirred at ambient temperature dissolves, under ice bath, temperature is down to 0 DEG C, start to drip a Grignard reagent [bromobenzene octyl ether (8.6g of bromobenzene octyl ether between brand-new, 30.2mmol), Mg (1g, 41.7mmol), THF (30ml)], after reaction 20min, start at 0 DEG C to drip oxalyl chloride (1.71g, 13.5mmol), dropwise, continue reaction 30min.Saturated NH4Cl solution cancellation reaction is added in system, extraction into ethyl acetate, salt water washing organic phase, anhydrous MgSO4 is dry, concentrated removal organic solvent, the thick product n-hexane/ethyl acetate obtained (volume ratio is 200:1) silica gel column chromatography, obtains 1,2-bis-(3-octyloxyphenyl) second diketone 3.46g, productive rate 55%.
The preparation of (3) 2,7-bis-octyloxy-9,10-phenanthrenequione (compound 3)
Under argon shield, 1,2-bis-(3-octyloxyphenyl) second diketone (0.70g, 1.5mmol) be dissolved in 80ml dry methylene chloride solution, add 0.25ml boron trifluoride diethyl etherate and trifluoro vanadyl (0.41g, 3.3mmol), 0 DEG C is stirred 10 minutes; Add molybdenum pentachloride (0.90g, 3.3mmol), stirring reaction 30min.The sodium hydrogen carbonate solution (50ml) of ice is added in system, suction filtration, extraction into ethyl acetate, anhydrous magnesium sulfate drying, concentrated removal organic solvent, the thick product n-hexane/ethyl acetate obtained (volume ratio is 100:1) silica gel column chromatography, obtain 2,7-bis-octyloxy-9,10-phenanthrenequione 0.56g, productive rate 80%.
(4) preparation of fluoro-10,13-bis-bromo-2, the 7-bis-octyloxy benzodiazepine anthracenes (compound 4) of 11-
Fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (0.59g, 1.9mmol) of 4-and 2,7-bis-octyloxy-9,10-phenanthrenequione (0.88g, 1.9mmol) are dissolved in 40ml acetic acid, are warming up to 60 DEG C, close heating, react 2h under room temperature.Suction filtration, washing with alcohol filter cake, obtains fluoro-10,13-bis-bromo-2, the 7-bis-octyloxy benzodiazepine anthracene 1.28g of 11-, productive rate 95%.Nuclear-magnetism characterization data is: 1HNMR (CDCl3,500MHz, ppm), δ: 8.40 (d, 2H), 8.04 (d, 2H), 7.84 (d, 1H), 7.15 (s, 2H), 4.09 (t, 4H), 1.85 (s, 4H), 1.37 (m, 20H), 0.85 (s, 6H).
Embodiment 2: polymer A
Reaction is carried out under nitrogen protection, 11-fluoro-10, 13-bis-bromo-2, 7-bis-octyloxy benzodiazepine anthracene (213.7mg, 0.3mmol) He 2, two (tin trimethyl) thiophene (198.6mg of 5-, 0.3mmol) be dissolved in 10ml toluene, logical nitrogen 0.5h, add catalyzer three (dibenzylideneacetone) two palladium (5.5mg) and part tri-o-tolyl phosphorus (9.8mg), heating is started after continuing ventilation 0.5h, back flow reaction 24h, system is naturally cooling at room temperature, dropwise add to sedimentation in methyl alcohol, filter, the polymkeric substance vacuum drying oven 50 DEG C collected dries 12h, the polymkeric substance obtained uses methyl alcohol successively, normal hexane, chloroform surname extraction, concentrated chloroform extracted solution, again drop to sedimentation in methyl alcohol, obtain polymer A 175mg, for atropurpureus fibrous solids, productive rate 88%, number-average molecular weight 192.38kDa, distribution coefficient 2.94.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, and Bu4NPF6 makes ionogen, in acetonitrile solvent, initial oxidation current potential through cyclic voltammetry polymer A film is 0.95V, and according to calculation formula-(4.72+ initial oxidation current potential/V) eV of HOMO energy level, the HOMO energy level obtaining polymer A is-5.67eV, see accompanying drawing 1, reduce 0.16eV than polymkeric substance D.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: the sandwich battery structure of PC71BM/PFN/Al, polymer A and acceptor material PC71BM are made photovoltaic cell according to weight ratio 1:3, useful area 0.16cm2, current-voltage test is carried out under NewportThermalOriel69911 simulated solar light source, utilize Keithley2611 source to show to gather, open circuit voltage is 0.92V, short-circuit current density 11.6mA/cm2, packing factor 54.1%, photoelectric transformation efficiency is 5.77%.
Embodiment 3: polymer B
With embodiment 2, short of electricity unit is changed into fluoro-10,13-bis-bromo-3, the 6-bis-octyloxy benzodiazepine anthracenes of 11-, adopt identical polymerization process to obtain polymer B, productive rate 76%, number-average molecular weight 153.67kDa, distribution coefficient 2.75.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag+ electrode is reference electrode, Bu4NPF6 makes ionogen, in acetonitrile solvent, can be-5.58eV through the HOMO of cyclic voltammetry polymer B film.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: the sandwich battery structure of PC71BM/LiF/Al, polymer B and acceptor material PC71BM are made photovoltaic cell according to certain weight ratio, useful area 0.16cm2, current-voltage test is carried out under NewportThermalOriel69911 simulated solar light source, Keithley2611 source is utilized to show to gather, open circuit voltage is 0.89V, and photoelectric transformation efficiency is 5.42%.
Embodiment 4: polymkeric substance C
With embodiment 3, short of electricity unit changes fluoro-10,13-bis-bromo-2,3,6, the 7-bis-octyloxy benzodiazepine anthracenes of 11-into, adopts identical polymerization process to obtain polymkeric substance C, productive rate 72%, number-average molecular weight 90.78kDa, distribution coefficient 2.43.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag +electrode is reference electrode, Bu 4nPF 6making ionogen, in acetonitrile solvent, can be-5.63eV through the HOMO of cyclic voltammetry polymkeric substance C film.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC 71the sandwich battery structure of BM/PFN/Al, by polymkeric substance C and acceptor material PC 71bM makes photovoltaic cell according to certain weight ratio, useful area 0.16cm 2, under NewportThermalOriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source to show to gather, open circuit voltage is 0.91V, and photoelectric transformation efficiency is 5.58%.
The HOMO energy level of table 1 polymkeric substance

Claims (4)

1. fluorine-containing phenanthrene is for a conjugated polymers for quinoxaline and thiophene, and it is characterized in that, general structure is such as formula shown in I:
In formula, R 1, R 2can identical also can be different;
Work as R 1during=H, R 2alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20;
Work as R 2during=H, R 1alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20;
Work as R 1=R 2time, be alkyl or the alkoxyl group of the straight or branched of 4 to 20.
2. fluorine-containing phenanthrene as claimed in claim 1 is for the conjugated polymers of quinoxaline and thiophene, it is characterized in that, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in II:
3. fluorine-containing phenanthrene as claimed in claim 1 is for the conjugated polymers of quinoxaline and thiophene, it is characterized in that, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in III:
4. fluorine-containing phenanthrene as claimed in claim 1 is for the conjugated polymers of quinoxaline and thiophene, it is characterized in that, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in IV:
CN201510449945.6A 2015-07-28 2015-07-28 Fluorine-containing phenanthrene is for quinoxaline and the conjugated polymer of thiophene Expired - Fee Related CN105061730B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276559A (en) * 2018-01-16 2018-07-13 华南协同创新研究院 It is a kind of containing three heterocyclic conjugated polymer of phenanthro- and its application in organic electro-optic device
WO2018131766A1 (en) * 2017-01-10 2018-07-19 건국대학교 산학협력단 Phenazine derivative having increased solubility, and polymer for organic photovoltaic conversion device, using same
CN108976392A (en) * 2018-05-28 2018-12-11 华南师范大学 The conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline and its application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102159617A (en) * 2008-09-19 2011-08-17 默克专利股份有限公司 Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors
CN103724283A (en) * 2013-12-17 2014-04-16 华南理工大学 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer, preparation method of 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer and polymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102159617A (en) * 2008-09-19 2011-08-17 默克专利股份有限公司 Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors
CN103724283A (en) * 2013-12-17 2014-04-16 华南理工大学 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer, preparation method of 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer and polymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RENEE KROON ET AL.: ""New quinoxaline and pyridopyrazine-based polymers for solution-processable photovoltaics"", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018131766A1 (en) * 2017-01-10 2018-07-19 건국대학교 산학협력단 Phenazine derivative having increased solubility, and polymer for organic photovoltaic conversion device, using same
CN108276559A (en) * 2018-01-16 2018-07-13 华南协同创新研究院 It is a kind of containing three heterocyclic conjugated polymer of phenanthro- and its application in organic electro-optic device
CN108276559B (en) * 2018-01-16 2020-01-17 华南协同创新研究院 Phenanthro-containing tri-heterocyclic conjugated polymer and application thereof in organic photoelectric device
CN108976392A (en) * 2018-05-28 2018-12-11 华南师范大学 The conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline and its application

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