CN115584017A - Biisothiazole wide band gap polymer and application thereof in photoelectric device - Google Patents
Biisothiazole wide band gap polymer and application thereof in photoelectric device Download PDFInfo
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- CN115584017A CN115584017A CN202211214413.0A CN202211214413A CN115584017A CN 115584017 A CN115584017 A CN 115584017A CN 202211214413 A CN202211214413 A CN 202211214413A CN 115584017 A CN115584017 A CN 115584017A
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- bithiazole
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- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 33
- SMSLWFZHCONMGQ-UHFFFAOYSA-N 2-(1,3-thiazol-2-yl)-1,3-thiazole Chemical compound C1=CSC(C=2SC=CN=2)=N1 SMSLWFZHCONMGQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 230000002950 deficient Effects 0.000 claims abstract description 9
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- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004185 ester group Chemical group 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
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- YOWKNNKTQWCYNC-UHFFFAOYSA-N methyl 2-bromo-1,3-thiazole-4-carboxylate Chemical compound COC(=O)C1=CSC(Br)=N1 YOWKNNKTQWCYNC-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
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- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 claims description 2
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- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 4
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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Abstract
The invention discloses a bithiazole-like wide-band gap polymer, which comprises an electron donor unit and an electron deficient unit, wherein the electron deficient unit adopts a bithiazole-containing monomer; the structural formula is shown as formula I or formula II:
wherein R is selected from F, cl, OR 3 Methyl or ester group, wherein R 3 Selected from alkyl chains of different lengths (C) 1 ～C 30 ) (ii) a Ar is selected from furan, thiophene, stannophene or bithiophene; n is 10-100. The polymer material takes bithiazole as an electron-deficient unit (A) and is a polymer material copolymerized with different electron-donating units; the material has better absorption, deeper highest occupied empty orbit and better planarity within the band gap range of 1.8-2.2 eV, and the related preparation cost is lower and the steps are simple; can be used as an electron donor material or an electron transport layer material in the field of photoelectric devices such as organic solar cells, perovskite solar cells and the likeHas good commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials and devices thereof, and particularly relates to a bithiazole wide band gap polymer and application thereof in photoelectric devices.
Background
The rapid development of society cannot avoid the consumption of various energy sources, but both fossil energy sources and nuclear energy sources inevitably face severe problems, such as energy shortage, environmental pollution, safe use and the like. Therefore, the demand for green clean energy is increasingly pressing. Among them, solar energy is regarded as a green and pollution-free renewable energy source. Research on organic solar cells has attracted extensive attention in academia and society in recent years as a device capable of converting light energy into electric energy. Compared with the traditional inorganic semiconductor solar cell, the organic solar cell has many advantages, such as low cost, light weight, simple preparation process, capability of being prepared into semitransparent devices, flexible devices and the like, and shows high research value and considerable application prospect.
In order to realize high efficiency organic photovoltaic materials, photovoltaic parameters (FF, J) are required sc 、V oc ) And (4) maximizing. And the parameters can be improved by methods such as additives, forward and reverse structures of devices, heat treatment and the like. But most importantly, the effective regulation and control of the band gap, the energy level and the morphology of the polymer are realized by optimizing the structure of the donor-acceptor unit. In particular, the rapid rise of non-fullerene small molecule acceptor materials in recent years has broken the routine to improve the efficiency of battery devices to new heights, more than 18% (Sci.Bull., 2020,65,272-275 adv.Mater.,2020,32,1908205. In the reported high-performance organic solar cell, compared with the fullerene acceptor material, the absorption spectrum width of the non-fullerene small molecule acceptor material can be expanded to a near infrared region (about 1000 nm), and excitons in the organic photovoltaic material can be efficiently separated under the drive of lower charge separation to generate charges. Therefore, how to improve photon utilization while reducing energy loss is the key of efficient photovoltaic material design. Based on the advantages exhibited by non-fullerene acceptor small molecules, there is a great need to design a class of polymer donor materials to better match non-fullerene acceptors at energy levels, resulting in lower energy loss (V) loss ) Thereby to makeA higher PCE is implemented.
Disclosure of Invention
The invention mainly aims to provide a wide-bandgap polymer taking bithiazole as an A unit aiming at the defects in the prior art, and the wide-bandgap polymer has the advantages of simple preparation steps, low cost, good planarity, capability of being prepared in a large scale, lower HOMO (highest occupied molecular orbital), higher open-circuit voltage, energy level matching with an electron acceptor material, complementary absorption, smaller energy loss, higher charge mobility and the like, can be used as an electron donor material or an electron transport layer material, and has good commercial application prospect in the field of photoelectric devices such as organic solar cells, perovskite solar cells and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a series of bithiazole wide-band gap polymers, which comprise an electron donor unit (D unit) and an electron deficient unit (A unit), wherein the electron deficient unit adopts a bithiazole-containing monomer; the structural formula is shown as formula I or formula II:
wherein R is selected from F, cl, OR 3 Methyl or ester group, wherein R 3 Selected from alkyl chains of different lengths (C) 1 ～C 30 ) (ii) a Ar is selected from furan, thiophene, stannophene or bithiophene; n is 10-100.
In the scheme, the molecular weight of the bithiazole wide-band gap polymer is 1-50 ten thousand.
Further, the structural formula of the electron donating unit (D unit) is selected from the following;
wherein R is 2 Selected from alkyl chain with carbon number of 1-30; x is H, F or Cl; x 1 Selected from H, F or Cl.
In the scheme, the structural formula of the monomer containing the bithiazolyl is shown as a formula IV;
wherein R is selected from F, cl and OR 1 Methyl or ester group (R) 1 Selected from alkyl chains of different lengths (C) 1 ～C 30 ) (ii) a Ar is selected from furan, thiophene, stannophene or bithiophene.
The preparation method of the bithiazole wide-bandgap polymer comprises the following steps: adding an electron donor unit monomer, a monomer containing a bithiazolyl group and a catalyst into an organic solvent, uniformly mixing, and reacting for 24-72 hours at 110-150 ℃ under a protective atmosphere; wherein the molar ratio of the D unit monomer to the A unit monomer to the catalyst is 1:1 (0.02-0.05).
In the above scheme, the structural formula of the electron donor unit monomer (D unit monomer) is shown as one of formula V:
in the formula (I); r 2 Selected from alkyl chain with carbon number of 1-30; x is H, F or Cl; x 1 Selected from H, F or Cl; y is O, S or Se.
In the above scheme, the catalyst is tetrakis (triphenylphosphine) palladium or tris dibenzylideneacetone dipalladium; the organic solvent is toluene, chlorobenzene or o-xylene.
In the above scheme, the protective atmosphere may be an atmosphere such as nitrogen.
In the above scheme, the preparation method of the electron-deficient unit monomer (a unit monomer) comprises the following steps: reacting 2-bromothiazole-4-carboxylic acid methyl ester under the catalysis condition of silver fluoride and dibenzonitrile palladium dichloride to generate a white solid; then carrying out coupling reaction with tin thiophene salt to generate oily liquid; then adding cerium oxide and alkyl alcohol to generate oily liquid; finally NBS reaction produces the final A unit monomer.
In the above scheme, the reaction process for generating the white solid comprises: mixing 2-bromothiazole-4-carboxylic acid methyl ester, diphenylnitrile palladium dichloride and a solvent, adding part of silver fluoride, and stirring and reacting for 6-12 h at the temperature of 60-120 ℃; then adding the rest silver fluoride, and continuously stirring and reacting for 6-12 h at the temperature of 60-120 ℃.
In the scheme, the molar ratio of the methyl 2-bromothiazole-4-carboxylate, the silver fluoride and the diphenylnitrile palladium dichloride is 1:1-2 and is 0.05-0.2.
In the above aspect, the alkyl alcohol has 1 to 30 carbon atoms.
In the above embodiment, the preparation method of the electron donor unit monomer (D unit monomer) comprises the following steps:
under the anhydrous and oxygen-free conditions, halogenated thiophene is dissolved in Tetrahydrofuran (THF), equimolar amount of Lithium Diisopropylamide (LDA) is dropwise added, reaction is carried out at normal temperature for 1-1.5 h, then bromoalkane is added, and reflux stirring is carried out overnight; then quenching by adopting water, extracting, drying to remove the solvent, and distilling under reduced pressure to obtain colorless oily liquid; then adding tetrahydrofuran under the protective atmosphere, adding lithium diisopropylamide with equimolar amount under ice bath for reaction for 1-1.5 h, then recovering to room temperature, adding BDT, heating to 40-50 ℃, reacting for 1.5-2 h, then cooling to room temperature, adding SnCl 2 And hydrochloric acid, reflux overnight; quenching with water, extracting, drying, removing solvent by rotary evaporation, separating and purifying by silica gel column chromatography, and eluting with petroleum ether to obtain yellow solid; finally dissolving the mixture in tetrahydrofuran, adding n-butyllithium to react for 1-2 h at-78 ℃, adding trimethyl tin chloride to react for 0.5-1 h, and heating to room temperature to react overnight; preparing D unit monomer or adding n-butyl lithium into the monomer to react for 1-2 h at-78 ℃, adding trimethyl tin chloride to react for 0.5-1 h, heating to room temperature to react overnight to prepare D unit monomer.
In the scheme, the number of carbon atoms of the brominated alkane is 1-20.
The invention also includes the use of a wide bandgap polymer with electron donating units and bithiazole as a units as an active layer material or a transport layer material in an optoelectronic device.
Specifically, the wide bandgap polymer material can be used for organic solar cells, perovskite solar cells, organic light emitting diodes, organic detectors, and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) Halogen atoms, methyl or ester groups and the like are introduced, so that the HOMO energy level of the polymer can be effectively reduced, the open-circuit voltage is improved, pi-pi accumulation can be increased, and charge transmission is facilitated; the bithiazole introduced by the invention can effectively reduce HOMO energy level, and provide larger Voc and smaller E loss (ii) a The double bonds C = N can enable the pi-pi accumulation of the polymer to be better, effectively improve the crystallization performance of the polymer and improve the charge transmission performance; the more planar structure also causes the red shift of the light absorption capacity of the polymer, can be better matched with the absorption of a receptor, and improves Jsc; after monomer units such as thiophene or selenophene are connected, the pi-pi accumulation of the polymer can be further increased, and the photovoltaic performance of the polymer is improved. The planarity and the stacking property of molecules can be effectively improved by C = N double bonds in the bithiazole, monomer units such as thiophene and selenophene are further introduced, the HOMO energy level and the light absorption capacity can be adjusted, and the obtained polymer donor can be well matched with the energy level and the absorption of an acceptor; and can increase the pi-pi accumulation of the polymer after connecting the thiophene or selenophene monomer units, so that the ultraviolet absorption red shift is realized, the light absorption capacity is improved, and the J is improved SC (ii) a The introduced D unit can further reduce the HOMO energy level, improve the planarity, ensure better crystallization performance and be more beneficial to charge transmission; the obtained polymer is a wide-bandgap polymer, and has better energy conversion efficiency with a non-fullerene receptor compared with a narrow-bandgap polymer; the organic solar cell can be used as a donor material and applied to an organic solar cell, so that the photoelectric conversion efficiency can be effectively improved;
2) The unit A in the wide-bandgap polymer material is cheap in raw materials, simple in preparation steps and capable of being prepared in large scale.
Drawings
FIG. 1 shows UV-visible absorption spectra of the polymer 6 obtained according to the present invention in the states of an o-dichlorobenzene solution (room temperature) and a thin film, respectively.
FIG. 2 is an electrochemical cyclic voltammogram of the polymer 6 obtained in the present invention, using a 0.1M aqueous acetonitrile solution of tetrabutylammonium hexafluorophosphate as an electrolyte solution, and a scanning rate of 0.1V/s.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A wide band gap polymer with bithiophene as a D unit and bithiazole as an A unit is prepared by the following steps:
(1) The preparation of the electronic unit-lacking monomer of the bithiazole comprises the following synthetic route:
the preparation method comprises the following specific steps:
1-1) methyl 2-bromothiazole-4-carboxylate (200mg, 0.9mmol) and PdCl 2 (PhCN) 2 (34mg, 0.09mmol) and DMSO (10 mL) were added to a 20mL Schlenk tube equipped with a magnetic stir bar; a portion of AgF (114mg, 0.9mmol) was added, the resulting mixture was heated at 60 ℃ and stirred for 3h, then AgF (114mg, 0.9mmol) was added and stirring continued at 60 ℃ for 3h; after the reaction, the mixture was extracted with dichloromethane and saturated NaCl, and the organic phases were combined and washed with anhydrous NaSO 4 After drying, removing the solvent; purification by column chromatography on silica gel eluting with petroleum ether/ethyl acetate (5:1) gave compound 1 as a white solid (0.198g, 45%);
1-2) Compound 1 (1.1g, 2.5 mmol), 2-Tributylstannyl thiophene (2.05g, 5.5 mmol) and Pd (PPh) under anhydrous and oxygen-free conditions 3 ) 4 (0.289g, 0.25mmol) in 30mL of toluene and refluxing overnight; after the reaction, after quenching with distilled water, extraction with saturated sodium chloride and dichloromethane, the organic phase was extracted with anhydrous NaSO 4 After drying, removing the solvent; separating and purifying with silica gel column chromatography, eluting with petroleum ether/dichloro-benzeneMethane (1:2 by volume) gave compound 2 as a yellow oil (0.81 g, 72% yield);
1-3) dissolving compound 2 (0.448g, 1mmol), 2-n-octane-1-dodecanol (0.596g, 2mmol) and cerium oxide (0.412g, 2.4 mmol) in 10mL of toluene under anhydrous and oxygen-free conditions, and refluxing overnight; after the reaction is finished, extracting by using a large amount of water and petroleum ether, and using anhydrous NaSO for an organic phase 4 Drying and then removing the solvent by rotary evaporation; the crude product was purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane (1:1 by volume) to give compound 3 as a yellow oily liquid (0.762 g, 80% yield);
1-4) dissolving the compound 3 (0.953g and 1mmol) in trichloromethane and acetic acid (the volume ratio is 1:1), adding NBS (0.356g and 2mmol) at normal temperature after dissolving, and reacting overnight; quenching with deionized water, adding dichloromethane for extraction, and extracting with anhydrous NaSO 4 After drying, the solvent was removed and purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane (2:1 by volume) as yellow oily liquid 4 (0.943 g, 85% yield)
(2) The specific synthetic route of the preparation of the bithiophene electron-donating unit is as follows:
the preparation method comprises the following specific steps:
3,3 '-difluoro-2,2' -bithiophene (0.202g, 1mmol) is dissolved in 30mL THF under anhydrous and oxygen-free conditions, n-butyllithium (2.1 mmol) is added at-78 ℃ for reaction for 1h; subsequently, trimethyltin chloride (0.498g, 2.5 mmol) was added thereto, and after a reaction for 30min, the temperature was raised to room temperature overnight; after the reaction is finished, quenching by distilled water, extracting by dichloromethane and saturated NaCl solution, and then adding anhydrous NaSO 4 After drying, the solvent was removed by rotary evaporation and the product was obtained by vacuum pump drainage as 5 (0.421 g, 80% yield);
(3) The preparation of the wide band gap polymer has the following synthetic route:
the preparation method comprises the following specific steps:
under the protection of nitrogen, compound 4 (0.222g, 0.2mmol) and compound 5 (0.105g, 0.2mmol) are added in sequence, and catalyst Pd (PPh) 3 ) 4 (0.012g, 0.01mmol) and 5mL of anhydrous toluene, and reacting at 120 ℃ for 48h; settling the crude product by using methanol, and then sequentially extracting by using acetone, normal hexane, dichloromethane and trichloromethane; chloroform was rotary evaporated, methanol was added for settling, and suction filtered to give the final wide bandgap polymer product 6 (0.177 g, 75% yield).
FIG. 1 shows the UV-visible absorption spectra of the polymer 6 obtained according to the present invention in the states of an o-dichlorobenzene solution (room temperature) and a thin film, respectively; wherein the preparation steps of the polymer film are as follows: the obtained polymer 6 is dissolved in chloroform to prepare a solution with the concentration of 0.1g/mL, and then a film with the thickness of 80-160 nm is obtained by rotary evaporation coating. As can be seen from fig. 1: at a concentration of 10 -2 In mg/mL o-dichlorobenzene solution, the obtained polymer 6 shows two characteristic absorption peaks, wherein the absorption peak with the short wavelength is 350nm, and is attributed to pi-pi electron transition of side chains in the compound; the absorption peak at the long wavelength is located at 536nm and is attributed to pi-pi electron transition of a main body structure in the compound; in addition, the absorption peak at 566nm appears as a shoulder peak, and the absorption coefficient is slightly higher than that at a long wavelength.
In the film state, the characteristic peak displayed by the polymer 6 is red-shifted by 12nm compared with that in the solution state, and meanwhile, the absorption range is widened, and the shoulder peak is higher, which indicates that the formed film structure has stronger pi-pi accumulation and is beneficial to obtaining high carrier mobility. Polymer 6 film edge absorption was 652nm according to equation E g Calculated as = 1240/lambda, bandgap E g 1.90eV, and is a wide bandgap polymer.
The redox process of the polymer 6 is tested by using an electrochemical cyclic voltammetry method to obtain an initial redox potential relative to ferrocene, and then front line orbital energy levels (HUMO energy level and LUMO energy level) of a corresponding material are estimated, and the method specifically comprises the following steps: adopting a three-electrode system, dissolving the synthesized polymer 6 in chloroform to prepareA solution with the concentration of 5mg/mL is dripped on a glassy carbon electrode to prepare a thin film, and then the thin film is placed in an acetonitrile electrolyte solution containing 0.1M tetrabutylammonium hexafluorophosphate for testing, nitrogen protection is required in the whole process of testing, and the scanning speed is 0.1V/s, and the result is shown in figure 2. As can be seen from fig. 2: the polymer 6 has an irreversible redox process at the anode, corresponding to an initial oxidation potential of 0.73V. According to the formula HUMO = - (E) Ox,onset + 4.8) eV, we can calculate the HUMO energy level of polymer 6 to be-5.53 eV. The LUMO level is obtained to-3.63 eV (LUMO = HUMO + Eg) depending on the optical bandgap and HUMO of the material.
It can be seen from fig. 1 and 2 that the polymer 6 has good energy level matching and complementary absorption with the reported non-fullerene acceptor material Y6, and the prepared device can obtain higher open-circuit voltage and smaller energy loss. The polymer 6 obtained by the invention is used as a donor material to be applied to an organic solar cell, so that higher photoelectric efficiency can be obtained.
Example 2
A wide-band gap polymer with chloroBDT as D unit and bithiazole as A unit is prepared through the following steps:
(1) The preparation of the chloroBDT electron donor unit comprises the following specific synthetic route:
the preparation method comprises the following specific steps:
1-1) dissolving 3-chlorothiophene (4.74g, 40mmol) in 50mL of anhydrous THF under anhydrous and oxygen-free conditions, slowly and uniformly dripping equimolar Lithium Diisopropylamide (LDA), reacting at normal temperature for 1h, adding bromoisooctane (8.5 g, 44mmol), and stirring at 40 ℃ overnight; after the reaction is finished, quenching by deionized water, extracting by petroleum ether, and then using anhydrous NaSO 4 After drying, the solvent was removed and distillation was performed under reduced pressure to obtain compound 8 (8.49 g, yield 92%) as a colorless oily liquid;
1-2) adding 50mL of THF and a compound 7 (2.03g, 8.8mmol) under the protection of nitrogen, and adding an equivalent amount of LDA under ice bath for reaction for 1h; followed byBDT (0.881g, 4 mmol) is added after returning to room temperature, and the temperature is raised to 50 ℃ for reaction for 1.5h. Then, cooling to room temperature, adding SnCl 2 ·2H 2 O (7.22g, 32mmol) and 10mL of 10% HCl were refluxed overnight. Quenching with deionized water, adding petroleum ether for extraction, and extracting with anhydrous NaSO 4 Drying, rotary evaporating to remove solvent, and separating and purifying by silica gel column chromatography with petroleum ether as eluent to obtain compound 9 (2.33 g, 89.9% yield) as yellow solid;
1-3) dissolving yellow solid 8 (1.295g, 2mmol) in 30mL THF under anhydrous and oxygen-free conditions, and adding n-butyllithium (4.4 mmol) for reaction at-78 ℃ for 1h; subsequently, trimethyltin chloride (0.896 g,4.5 mmol) was added and reacted for 30min, followed by warming to room temperature overnight; after the reaction is finished, quenching by distilled water, extracting by dichloromethane and saturated NaCl solution, and then adding anhydrous NaSO 4 After drying, the solvent was removed by rotary evaporation and the product 10 (1.27 g, 85.2% yield) was obtained by vacuum pump suction.
(2) The preparation of the wide band gap polymer has the following synthetic route:
the preparation method comprises the following specific steps:
under the protection of nitrogen, compound 4 (0.222g, 0.2mmol) and compound 10 (0.195g, 0.2mmol) were added in sequence, and Pd (PPh) as a catalyst 3 ) 4 (0.012g, 0.01mmol) and 5mL of anhydrous toluene, and reacting at 120 ℃ for 48h; settling the crude product by using methanol, and then sequentially extracting by using acetone, normal hexane, dichloromethane and trichloromethane; chloroform was rotary evaporated, methanol was added for precipitation, and the final wide bandgap polymer product 6 (0.28 g, 86% yield) was obtained by suction filtration.
Comparative example 1
An attempt was made to synthesize compound 1 using an alternative route, with the following specific steps:
2-bromine is reacted withThiazole-4-carboxylic acid methyl ester (222.06mg, 1mmol), cuCl 2 (215.11mg, 1.6 mmol), LDA (1 mmol) and DMSO (10 mL) were added to a 20mL Schlenk tube equipped with a magnetic stir bar; the resulting mixture was heated at 120 ℃ with stirring overnight; after the reaction, the mixture was extracted with dichloromethane and saturated NaCl, and the organic phases were combined and washed with anhydrous NaSO 4 After drying, removing the solvent; the detection result shows that the obtained product is basically raw material and can not synthesize the target product.
The novel bithiazole wide-band gap polymer provided by the invention has high spectral absorption, energy level distribution and accumulation capacity, so that the polymer material can be widely applied to organic photoelectric materials. Meanwhile, the thiazole monomer can be further optimized, so that the thiazole monomer plays an important role in the aspect of photoelectron application.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (9)
1. The bithiazole wide-band gap polymer is characterized by comprising an electron donor unit and an electron deficient unit, wherein the electron deficient unit adopts a bithiazole-containing monomer; the structural formula is shown as formula I or formula II:
wherein R is selected from F, cl, OR 3 Methyl or ester group, wherein R 3 Selected from alkyl chains of varying lengths; ar is selected from furan, thiophene, stannophene or bithiophene; n is 10-100.
2. The wide bandgap polymer of claim 1, wherein the electron donating unit has a structural formula comprising;
wherein R is 2 Selected from alkyl chain with carbon number of 1-30; x is H, F or Cl; x 1 Selected from H, F or Cl.
3. The wide band gap bithiazole polymer of claim 1, wherein the bithiazolyl group-containing monomer has the structural formula IV;
wherein R is selected from F, cl, OR 1 Methyl or ester group (R) 1 Selected from alkyl chains of different lengths (C) 1 ～C 30 ) (ii) a Ar is selected from furan, thiophene, stannene or bithiophene.
4. A process for preparing a wide bandgap polymer of the bis-thiazoles according to any one of claims 1 to 3, comprising the steps of: adding an electron donor unit monomer, a monomer containing a bithiazolyl group and a catalyst into an organic solvent, uniformly mixing, and reacting for 24-72 hours at 110-150 ℃ under a protective atmosphere; wherein the molar ratio of the D unit monomer to the A unit monomer to the catalyst is 1:1 (0.02-0.05).
5. The method of claim 4, wherein the electron donating unit monomer has one of the following structural formulas:
in the formula (I); r 2 Selected from alkyl chain with carbon number of 1-30; x is H, F or Cl; x 1 Selected from H, F or Cl; y is O, S or Se.
6. The method according to claim 4, wherein the catalyst is tetrakis (triphenylphosphine) palladium or tris dibenzylideneacetone dipalladium; the organic solvent is toluene, chlorobenzene or o-xylene.
7. The process according to claim 4, wherein the process for preparing the electron-deficient unit monomer (A unit monomer) comprises the steps of: reacting 2-bromothiazole-4-carboxylic acid methyl ester under the catalytic condition of silver fluoride and diphenylnitrile palladium dichloride to generate a white solid; then carrying out coupling reaction with tin thiophene salt to generate oily liquid; then adding cerium oxide and alkyl alcohol to generate oily liquid; finally NBS reaction generates the final A unit monomer.
8. The method of claim 7, wherein the reaction to form a white solid comprises: mixing 2-bromothiazole-4-carboxylic acid methyl ester, diphenylnitrile palladium dichloride and a solvent, adding part of silver fluoride, and stirring and reacting for 6-12 h at the temperature of 60-120 ℃; then adding the rest silver fluoride, and continuously stirring and reacting for 6-12 h at the temperature of 60-120 ℃.
9. Use of a bithiazole wide bandgap polymer according to any one of claims 1 to 3 or a bithiazole wide bandgap polymer prepared by the preparation process according to any one of claims 4 to 8 in an opto-electronic device.
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