CN108976392A - The conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline and its application - Google Patents
The conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline and its application Download PDFInfo
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Abstract
The invention discloses a kind of conjugated polymer photoelectric material of condensed ring of acid imide containing quinoxaline and its applications, the material has the main chain and side-chain radical of conjugation, the wherein condensed cyclic structure of acid imide containing quinoxaline and other copolymerization units in conjugated main chain, side-chain radical include the alkyl chain R with enhancing polymer solubility.Due to polymer have conjugation backbone structure, electron cloud can on main polymer chain delocalization, so that polymer is shown characteristic of semiconductor, have photoelectric properties abundant；The solubilizing group R on polymer lateral chain can be dissolved in organic solvent simultaneously, suitable for preparing photoelectric device using printing, roll-to-roll or inkjet printing Solution processing techniques.The conjugated polymer of the condensed ring of acid imide containing quinoxaline can be applied as carrier blocking layers, N-type material, luminescent layer or photovoltaic active layers in photovoltaic, luminous or field effect transistor photoelectric device.
Description
Technical field
The present invention relates to a kind of conjugated polymer and macromolecule photoelectric Material Field, in particular to acid imide containing quinoxaline is thick
The conjugated polymer photoelectric material of ring and its application.
Background technique
The development of organic/polymer photoelectric material provides new approach for the preparation of low cost, large area optoelectronic device.
Late 1970s, Alan J.Heeger etc. (Nobel chemistry Prize winner in 2000) have invented conducting polymer, thoroughly
The organic material based on carbon atom has been overturned as the traditional concept of insulator, has opened organic/polymer semiconductor's electronics
This emerging scientific domain is learned, so far the light of organic material, electricity, magnetic property gradually start to be recognized by the mankind, while being based on it
Various photoelectric devices also result in the concern of people.Organic/polymer semiconductor's photoelectric material not only has metal or half
The characteristic electron of conductor, and being easily worked much than metal or crystalline semiconductor, that processes electronic material at low temperature can
Energy property brings hope to cheap processing electronic device.More importantly organic/polymer semiconducting material of solution processable
It can be used as electronics " ink ", combining with conventional printing techniques (inkjet printing, offset printing etc.) sends out the manufacture of electronic device
Raw revolution, while the electronic device based on organic/polymer semiconductor's photoelectric material can also realize some special mechanics of needs
The application (such as flexible device) of property.Due to these special advantages, organic/polymer photoelectric material is very suitable for industrializing
Production and popularization, have very vast Commercial Prospect.
Since Deng's high official position study group of Kodak [Tang, C.W. in 1987；Van Slyke S. Aet.al；
Appl.Phys.Lett.1987,51,913. small organic molecule membrane electro luminescent device and nineteen ninety Britain Camb] are proposed
University research group R.H.Friend [Burroughes, J.H.； Bradley,D.D.C.；Friend,R.H；Holmes,
A.B.et.Al；Nature 1990,347,539.] propose organic polymer thin film electroluminescent device since, organic plate
Display technology obtains huge progress, has stepped into the industrialization stage at present, becomes the next-generation for replacing liquid crystal display.
At the same time, the organic photoelectrics such as organic photovoltaic cell, organic field effect tube, organic-biological and chemical sensor field
It obtains and flourishes.Especially in recent years, since energy consumption is growing day by day and requirement to low-carbon environment-friendly, coal petroleum gas
Equal traditional energies reserves are limited, and have pollution, emission greenhouse gas, therefore using solar energy as the renewable clear energy sources of representative
It is increasingly valued by the people, organic sun hull cell is very burning hot, and the efficiency frequency of nearest 2 years organic thin film cells is innovated
Height is had an optimistic view of by industry, and market-oriented prospect is very bright.
In numerous photoelectric materials, the photoelectric material containing quinoxaline and acid imide unit (chemical structure is as shown below)
In organic electroluminescent, organic photovoltaic cell has been obtained in the materials such as chemistry and biosensor and organic field effect tube
To being widely applied [Guo X.et.Al； Chem.Rev.,2014,114,8943；Chen J.et.Al；Acc.Chem.Res.,
2009,42, 1709.].When quinoxaline and acid imide unit construct conjugated polymer individually as copolymerization units, gather
Lowest unocccupied molecular orbital (LUMO) energy level and highest occupied molecular orbital(HOMO) (HOMO) energy level for closing object are not low enough, limit it
Application range, such as cannot function as N- type semiconductor material or polymeric acceptor is applied to field effect transistor, organic photovoltaic cell
In equal photoelectric devices.
It is an object of the invention to for prior art there are the shortcomings that, develop a kind of condensed cyclic structure with bigger plane
Both quinoxaline and acid imide (chemical structure is as follows) and its quinoxaline and imido conjugated polymer photoelectric material had been contained.With
Quinoxaline is compared with acid imide, and simultaneously acid imide is the structure being connected by quinoxaline and acid imide to quinoxaline, therefore it has quinoline
Quinoline and while acid imide advantage, also has a bigger rigid plane, stronger electron-withdrawing ability, lower minimum not occupy point
Some properties such as sub-track (LUMO) energy level and highest occupied molecular orbital(HOMO) (HOMO) energy level.To sum up it is expected that containing quinoline
Quinoline and imido conjugated polymer photoelectric material will have good photoelectric properties is that a kind of have commercial applications prospect
Material.However containing quinoxaline and imido conjugated polymer photoelectric material as a kind of promising photoelectric material is at present
Only in the field, someone is not reported, the present invention has synthesized novel quinoxaline and acid imide condensed ring unit and its polymer for the first time
And it is successfully applied in field of photovoltaic materials, resulting materials, which are applied to photoelectric device, has good photoelectric properties.
Summary of the invention
It is an object of the invention to for prior art there are the shortcomings that, a kind of being total to for condensed ring of acid imide containing quinoxaline is provided
Conjugated polymer photoelectric material and its application have good absorption, lowest unocccupied molecular orbital energy level and highest to sunlight
It is adjustable to occupy molecular orbital energy level, can be applied to production polymer solar cells active layer.
Of the invention provides a kind of technical solution are as follows:
The conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline, has the following structure:
Wherein, the natural number that n is 1~10000；The natural number that x is 1~10000；The natural number that y is 1~10000；A1,
A2 is same or different substituent group；B1, B2 are same or different oxygen atom, sulphur atom；C is conjugate unit component；R
For solubilizing group.
As a kind of perferred technical scheme, the conjugate unit component C have the following structure more than one:
As a kind of perferred technical scheme, the solubilizing group R is the alkyl of C1~C40 or the alcoxyl of C1~C40
Base, wherein on alkyl one or more carbon atoms by oxygen atom, alkenyl, alkynyl, aryl, ester group, itrile group, amido, quaternary ammonium salt base
Group, amine oxide, diethanol amine, pyridine oxide, quaternary phosphonium salt groups, phosphate radical, phosphate-based, sulfonate radical, carboxyl, one in hydroxyl
Kind or more functional group replace, hydrogen atom replaced by one or more of fluorine atom, chlorine atom, bromine atom, iodine atom functional group.
As a kind of perferred technical scheme, the substituent A 1, A2 be same or different hydrogen atom, chlorine atom,
Fluorine atom, nitro, alkyl, alkoxy, itrile group more than one.
The present invention provides another technical solution, and the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline is answered
With.
As a kind of perferred technical scheme, the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline is molten
Solution is processed into polymer film in organic solvent, by spin coating, printing, roll-to-roll or inkjet printing solution, as carrier transport
Layer, N-type material, luminescent layer or photovoltaic active layers are applied in photovoltaic, luminous or field effect transistor photoelectric device.
As a kind of perferred technical scheme, the photovoltaic device is by substrate, cathode, cathode interface layer, light absorbing layer, sun
Pole boundary layer, anode are stacked gradually and are constituted by substrate, anode, anode interface layer, light absorbing layer, cathode interface layer, cathode.
As a kind of perferred technical scheme, the anode material is preferably metal oxide, aluminium, silver, gold.
As a kind of perferred technical scheme, the anode interface layer is conjugatd polymers or inorganic semiconductor.
As a kind of perferred technical scheme, the cathode be metal, metal oxide, doping stannic oxide, zinc oxide,
Indium gallium zinc oxide or at least one of graphene and its derivative；The substrate is glass, flexible material, metal, alloy
Or at least one of stainless steel film.
In organic/polymer solar cells device (ITO cathode/electron transfer layer/photoactive layer/hole transmission layer/gold
Belong to anode or ito anode/hole transmission layer/photoactive layer/electron transfer layer/metallic cathode) in, above-mentioned acyl containing quinoxaline
The application method of the conjugated polymer photoelectric material of imines condensed ring: by the conjugated polymers object light of the condensed ring of acid imide containing quinoxaline
It is organic molten that electric material as acceptor material is dissolved in toluene, chloroform, chlorobenzene, dimethylbenzene etc. with other donor materials by a certain percentage
It in agent, is spun in ITO electrode and prepares photovoltaic active layers, pass through the techniques such as solvent, additive, solvent vapo(u)r processing, thermal annealing
Regulation forms it into the appearance structure for being conducive to carrier separation, transmission, collection, realizes high efficiency polymer solar battery.
The polymer not only has big conjugate planes, guarantees it with good carrier mobility；And two short of electricity subelements are simultaneously
Together, there is stronger electron-withdrawing ability, guarantee that polymer has lower HOMO and lumo energy；With proper conjugation unit
Copolymer, it is possible to obtain have red shift and broader absorption spectrum；The condensed ring of acid imide containing quinoxaline of this kind of new development
Conjugated polymer photoelectric material can be used as polymeric acceptor, and be possible to realize efficient all-polymer solar cell device.
Compared with prior art, the invention has the following advantages that
(1) quinoxaline acid imide condensed ring of the invention and its polymer are made of quinoxaline and acid imide unit, are had
Biggish conjugate planes structure is expected to interact by π-π supermolecule to form high-sequential and high carrier migration characteristic
The fill factor of polymer solar battery not only can be improved in thin polymer film, this characteristic, moreover it is possible to it is living to prepare thick film photovoltaic
Property layer, realize sunlight it is effective absorption and utilization.
(2) compared with traditional organic/polymer material, quinoxaline acid imide condensed ring of the invention and its polymer be by
Multiple short of electricity subelements simultaneously form together, have stronger electron deficient ability, so that polymer has lower HOMO, LUMO
Energy level, it may be possible to which the N-type polymer material of a kind of high electron mobility can be used as polymeric acceptor and be applied to polymer too
In positive energy battery.
(3) quinoxaline acid imide condensed ring is strong electron deficient functional group, is copolymerized with suitable unit, and can get has near-infrared
The material of absorption is blended with broad-band gap, intermediate band gap polymeric donor, and the photovoltaic active layers film of light absorption complementation can be obtained,
It realizes the effective use of sunlight, improves photoelectric current.
Detailed description of the invention
Fig. 1 is the bromo- 2- alkyl quinoxaline of title intermediate 5,8- bis- and imido nuclear magnetic resonance synthesized by embodiment 1
Map (1H NMR)。
Fig. 2 is the bromo- 2- alkyl quinoxaline of title intermediate 5,8- bis- and imido nuclear magnetic resonance synthesized by embodiment 1
Map (13C NMR)。
Fig. 3 is ultraviolet-visible light (UV) absorbance curve figure of 1 solid film of polymer P synthesized by embodiment 1.
Fig. 4 is the aerial photoelectron spectroscopy figure PESA of 1 solid film of polymer P synthesized by embodiment 1.
Fig. 5 is the chemical structural drawing of polymer P TB7-Th and PFN-Br.
Fig. 6 is that P1, P2 are electron acceptor, and PTB7-Th is the polymer solar cells device of electron donor in illumination condition
Lower current -voltage curve, device architecture are ITO cathode/cathode interface layer/active layer/sun machine boundary layer/anode.
Fig. 7 is polymer solar cells device junction composition.
Specific embodiment
Below by specific embodiment, the present invention is further illustrated, and its object is to help to better understand this hair
Bright content specifically includes materials synthesis, characterization and device and prepares, but these specific embodiments do not limit this in any way
The protection scope of invention.
The universal synthesis method of the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline: first synthesis contains and helps
Double bromine quinoxaline acid imide condensed ring monomers of molten alkyl chain, functionalization group, by with double tin trimethyls (or double borates)
Reagent obtains the polymer under the action of palladium catalyst, passes through control reaction time, temperature, solvent, catalyst, ligand etc.
Optimization can control the molecular weight and the coefficient of dispersion of polymer, and synthetic route is as follows:
Synthesis containing hydrotropy alkyl chain, double bromine quinoxaline acid imide condensed ring of functionalization group mainly uses following two
Route:
Route one, synthetic route is as follows, and 2,3- dioxo succinic acids (1) are heated in acetic anhydride solvent through simultaneously ring
Reaction obtains 2,3,4,5- tetrone (2) of furans, and compound (2) reacts to obtain containing hydrotropy with alkylamine in THF and dichloride sulfoxide
Pyrrolidines -2,3 of alkyl chain, 4,5- tetrones (3), 3,6- dibromo diazosulfide derivatives (4) are made in sodium borohydride reduction agent
The derivative (5) of the base containing diamine is obtained under, compound (3) and compound (5) are contained under conditions of sodium acetate/acetic acid
Hydrotropy alkyl chain, functionalization group double bromine quinoxaline acid imide condensed ring subject monomers.Pass through among optimization in route one
The type of substituent group or substituent group A1, A2, B1, B2 on body, can regulate and control quinoxaline acid imide condensed ring and its polymer
Photoelectric property.
Route two, synthetic route is as follows, and 3,6- dibromo diazosulfide derivatives (4) are made in sodium borohydride reduction agent
The derivative (7) of the base containing diamine is obtained under, and then with 2,3- dioxo succinate (8) under conditions of sodium acetate/acetic acid
It obtains key intermediate (9), compound (9) back flow reaction in concentrated hydrochloric acid obtains quinoxaline carboxylic acid's derivative (10), Jin Er
Be heated to reflux in acetic anhydride solvent by and ring react to obtain quinoxaline acid anhydrides (11), compound (11) and alkylamine in THF and
Dichloride sulfoxide reacts to obtain the subject monomers of double bromine quinoxaline acid imide condensed ring containing hydrotropy alkyl chain, functionalization group:
Embodiment 1
The preparation of polymer photoelectric material poly- [5,8-2- alkyl quinoxaline and acid imide -2,5- thiophene] (referred to as P1)
Synthetic route is as follows:
(1) synthesis of the bromo- 1,2- o-phenylenediamine of 3,6- bis-:
By 5.88g 4,7- bis- bromo- 2,1,3- diazosulfide 4 is dissolved in 200mL ethyl alcohol, and ice water is cooling, is added portionwise
14.0g sodium borohydride.It after reacting 6h, pours into brine ice, filters.Dry the bromo- 1,2- of 2.44g yellow pellet-like solids 3,6- bis-
O-phenylenediamine 5, yield 46%.
(2) the bromo- 2- alkyl quinoxaline of 5,8- bis- and imido synthesis (alkyl is 2- butyl octyl):
By 2.65g 3, bromo- 1, the 2- o-phenylenediamine of 6- bis- is dissolved in 50mL acetic acid, and 0.72g sodium acetate and 3.8g alkane is added
Base pyrroles -2,3,4,5- tetrones (3), heating reflux reaction is for 24 hours.Reaction solution is poured into brine ice, dichloromethane is added with stirring
Alkane extraction, organic layer are washed with water, and merge organic phase.After magnesium sulfate is dry, decompression boils off solvent.Silica gel column chromatography purifies (petroleum
Ether: methylene chloride=5:1), obtain 4.6g subject monomers (4), yield 75%.The nuclear magnetic data of product is as follows:
1H NMR(300MHz,CDCl3, δ, ppm): 8.17 (s, 2H), 2.23 (d, 2H, J=6.0Hz), 2.0 (m, 1H),
1.39-1.26(m,16H),0.98-0.85(m,6H).13C NMR (75MHz,CDCl3,δ,ppm):163.1,146.26,
143.28,136.77,126.09,43.65, 37.29,31.95,29.75,28.56,26.37,23.13,22.79,14.23。
(3) synthesis of poly- [5,8-2- alkyl quinoxaline and acid imide -2,5- thiophene] (referred to as P1):
Under argon atmosphere, by 616mg 5, the bromo- 2- alkyl quinoxaline of 8- bis- and acid imide, the bis- (trimethyls of 409mg 2,5-
Tinbase) thiophene, 4.5mg tris(dibenzylideneacetone) dipalladium (Pd2 (dba) 3) and 9.0mg tri- (o-methyl-phenyl) phosphorus (P (o-
Tol) 3) it is dissolved in the in the mixed solvent of 10mL toluene and 5mL tetrahydrofuran.Under protection of argon gas, back flow reaction 20h is cooled to room
Reaction solution is instilled in 300mL methanol and is precipitated, filters to obtain blood red solid by Wen Hou.In Soxhlet extractor with acetone, methanol,
After n-hexane, methylene chloride extract for 24 hours respectively, last polymer is got off with chloroform, through 0.45 μm has machine filter after cooling
It after film filtering, precipitates, filters in methyl alcohol, vacuum drying.Obtain 430mg dark red solid poly- [5,8-2- alkyl quinoxaline and acyl
Imines -2,5- thiophene] (P1), yield 75%, Mn=38.2K, PDI=3.4.The nuclear magnetic data of polymer is as follows:
1H NMR(300MHz,CDCl3,δ,ppm):8.2(br,2H),6.7(br,2H),2.23 (br,2H),2.0(br,
1H),1.39-1.26(br,16H),0.98-0.85(br,6H)。
Embodiment 2
Polymer photoelectric material is poly- [5,8-2- alkyl quinoxaline and acid imide -2,5-3,4- difluoro thiophene] (referred to as P2)
Preparation
The synthesis of poly- [5,8-2- alkyl quinoxaline and acid imide -2,5-3,4- difluoro thiophene] (referred to as P2):
Under argon atmosphere, by 616mg 5, the bromo- 2- alkyl quinoxaline of 8- bis- and acid imide, the bis- (trimethyls of 447mg 2,5-
Tinbase) -3,4- difluoro thiophene, 4.5mg tris(dibenzylideneacetone) dipalladium (Pd2 (dba) 3) and 9.0mg tri- (o-methyl-phenyl)
Phosphorus (P (o-Tol) 3) is dissolved in the in the mixed solvent of 10mL toluene and 5mL tetrahydrofuran.Under protection of argon gas, back flow reaction 20h,
After being cooled to room temperature, reaction solution is instilled in 300mL methanol and is precipitated, blood red solid is filtered to obtain.With third in Soxhlet extractor
After ketone, methanol, n-hexane, methylene chloride extract for 24 hours respectively, last polymer is got off with chloroform, through 0.45 μm after cooling
Organic membrane filtration after, precipitate in methyl alcohol, filter, vacuum drying.Obtain poly- [the 5,8-2- alkyl quinoline of 460mg dark red solid
Quinoline and acid imide -2,5-3,4- difluoro thiophene] (P2), yield 77%, Mn=33.2K, PDI=3.1.The nuclear-magnetism of polymer
Data are as follows:
1H NMR(300MHz,CDCl3,δ,ppm):8.4(br,2H),2.25(br,2H),2.1 (br,1H),1.49-
1.29(br,16H),0.99-0.84(br,6H)。
Embodiment 3
Illustrate that this quasi polymer can be used as N-type or poly- for polymer P 1, P2 synthesized by the embodiment 1 and example 2
It closes object receptor and is applied to polymer solar cell device (ITO cathode/cathode interface layer/active layer/sun machine boundary layer/sun
Pole) in:
By ITO electro-conductive glass, square resistance~20 Europe/square centimeter, 15 millimeters × 15 millimeters square pieces of pre-cut.Successively
With acetone, micron level semiconductor special purpose detergent, deionized water, isopropanol ultrasonic cleaning, nitrogen, which is blown a whistle, is placed on constant temperature oven
It is spare.The PFN-Br that one layer of 5nm thickness of Tu is revolved on ITO, is then spin coated onto active layer material PTB7-Th/P1, PTB7-Th/P2, thick
About 100 nanometers of degree, MoO is finally deposited3With Al electrode.All preparation process provide nitrogen atmosphere glove box in into
Row.The current -voltage curve of prepared upside-down mounting battery device is as shown in fig. 6, relevant data are listed in Table 1.It can see
Out, the conjugated polymer of the condensed ring of acid imide containing quinoxaline of the present invention can greatly improve the electric current of battery device, mention
High battery efficiency.Mainly good balance is reached in fill factor, short circuit current and open-circuit voltage.
Table 1: when representative conjugated polymer P1, P2 are as electron acceptor material, the performance parameter of organic photovoltaic devices
Claims (10)
1. the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline, which is characterized in that have the following structure:
Wherein, the natural number that n is 1~10000；The natural number that x is 1~10000；The natural number that y is 1~10000；A1, A2 are
Same or different substituent group；B1, B2 are same or different oxygen atom, sulphur atom；C is conjugate unit component；R is to help
Molten group.
2. the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 1, which is characterized in that institute
State more than one that conjugate unit component C has the following structure:
3. the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 1, which is characterized in that institute
State the alkoxy of alkyl or C1~C40 that solubilizing group R is C1~C40, wherein on alkyl one or more carbon atoms by oxygen
Atom, alkenyl, alkynyl, aryl, ester group, itrile group, amido, quaternary ammonium salt group, amine oxide, diethanol amine, pyridine oxide, quaternary alkylphosphonium salt
One or more of group, phosphate radical, phosphate-based, sulfonate radical, carboxyl, hydroxyl functional group replace, and hydrogen atom is by fluorine atom, chlorine
One or more of atom, bromine atom, iodine atom functional group replaces.
4. the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 1, it is characterised in that institute
State substituent A 1, A2 is same or different hydrogen atom, chlorine atom, one kind of fluorine atom, nitro, alkyl, alkoxy, itrile group
More than.
5. the application of the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline.
6. the application of the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 5, feature
It is, the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline is dissolved in organic solvent, passes through spin coating, print
Brush, roll-to-roll or inkjet printing solution are processed into polymer film, as carrier blocking layers, N-type material, luminescent layer or photovoltaic
Active layer is applied in photovoltaic, luminous or field effect transistor photoelectric device.
7. the application of the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 6, feature
It is, the photovoltaic device is by substrate, cathode, cathode interface layer, light absorbing layer, anode interface layer, anode or by substrate, sun
Pole, anode interface layer, light absorbing layer, cathode interface layer, cathode stack gradually composition.
8. the application of the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 7, feature
It is, the anode material is preferably metal oxide, aluminium, silver, gold.
9. the application of the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 7, feature
It is, the anode interface layer is conjugatd polymers or inorganic semiconductor.
10. the application of the conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline according to claim 7, feature
It is, the cathode is metal, metal oxide, doping stannic oxide, zinc oxide, indium gallium zinc oxide or graphene and its spreads out
At least one of biology；The substrate is at least one of glass, flexible material, metal, alloy or stainless steel film.
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| CN115612115A (en) * | 2022-09-20 | 2023-01-17 | 广西民族师范学院 | Quinoxaline-based conjugated microporous polymer grafted graphene material, photoelectrochemical sensor, preparation method and rifampicin detection method |
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| WO2023179275A1 (en) * | 2022-03-23 | 2023-09-28 | 华南协同创新研究院 | Fused ring unit based on quinoxaline derivative, small molecule containing same, polymer, preparation methods and use |
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| CN112552313A (en) * | 2019-12-16 | 2021-03-26 | 华南理工大学 | Fused ring quinoxalinyl non-fullerene acceptor material and preparation method and application thereof |
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| WO2023179275A1 (en) * | 2022-03-23 | 2023-09-28 | 华南协同创新研究院 | Fused ring unit based on quinoxaline derivative, small molecule containing same, polymer, preparation methods and use |
| CN115612115A (en) * | 2022-09-20 | 2023-01-17 | 广西民族师范学院 | Quinoxaline-based conjugated microporous polymer grafted graphene material, photoelectrochemical sensor, preparation method and rifampicin detection method |
| CN115612115B (en) * | 2022-09-20 | 2023-07-21 | 广西民族师范学院 | Quinoxalinyl conjugated microporous polymer grafted graphene material, photoelectrochemical sensor, preparation method and rifampicin detection method |
| CN116444539A (en) * | 2023-03-13 | 2023-07-18 | 华南理工大学 | Asymmetric condensed ring unit based on naphthalene dithiadiazole derivative, small molecule containing unit, polymer and preparation method and application thereof |
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