CN110655653B - A-D-A type polymer with main chain containing metal element, preparation method and application thereof - Google Patents

A-D-A type polymer with main chain containing metal element, preparation method and application thereof Download PDF

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CN110655653B
CN110655653B CN201810715073.7A CN201810715073A CN110655653B CN 110655653 B CN110655653 B CN 110655653B CN 201810715073 A CN201810715073 A CN 201810715073A CN 110655653 B CN110655653 B CN 110655653B
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应磊
钟知鸣
彭沣
黄飞
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses an A-D-A type polymer with a main chain containing metal elements, a preparation method and application thereof. The preparation method takes the A-D-A unit as a core, takes the alkyne-metal compound-alkyne unit as a ligament, introduces metal atoms into the copolymer, and the prepared polymer has wide spectral range absorption and high carrier mobility. The A-D-A type polymer with the main chain containing metal elements can be used as an active layer and applied to an organic/polymer photoelectric detector, an organic/polymer solar cell or an organic/polymer field effect transistor.

Description

A-D-A type polymer with main chain containing metal element, preparation method and application thereof
Technical Field
The invention belongs to the field of organic semiconductors, and particularly relates to an A-D-A type polymer with a main chain containing metal elements, a preparation method and application thereof in organic/polymer photodetectors, organic/polymer solar cells, organic/polymer diodes and organic/polymer field effect transistors.
Background
The photoelectric detector is a component for converting optical signals into electric signals based on the photoelectric effect, and has important application in the fields of optical communication, image sensing, biomedical sensing, environmental monitoring, meteorology, military and the like. The photodetectors commonly used today are based essentially on inorganic semiconductor materials, such as Si-based, Ge-based, and InGaAs, etc.
Compared with inorganic materials, the organic/polymer material has the advantages of low cost, easy adjustment of absorption wavelength, film formation through a solution method and the like, so that the organic/polymer photodiode has the advantages of simple manufacturing process, low production cost, light weight, easy large-area preparation, realization of flexible devices and wide application prospect. Gong et al utilize a narrow-band conjugated polymer PDDTT and a fullerene derivative PC61BM blending to prepare a full-color photodetector with a spectral response range of 300-1150 nm, wherein the detection rate of the detector under zero bias voltage exceeds 1013cm Hz1/2W-1The overall performance of the device is superior to that of silicon-based devices [ Science,2009,325(5948): 1665-1667-]。
The A-D-A type polymer with the main chain containing the metal element has good energy level structure and solution processing characteristics, and is beneficial to meeting the requirement that an organic light detector works in short wave infrared, so that the A-D-A type polymer has great development potential and prospect in the field of organic light detectors.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention mainly aims to provide an A-D-A type polymer with a main chain containing metal elements. The introduction of metal atoms can provide intermetallic supramolecular action, induce molecular aggregation, and combine the strong D-A action of an electron supply D unit to effectively adjust the absorption spectrum of the polymer, thereby improving the external quantum efficiency of the polymer. The regular structure of the A-D-A type enables polymer molecules to be more ordered, is more beneficial to the accumulation of the polymer molecules, can further improve the mobility and red shift of an absorption spectrum, and is beneficial to improving the molecular weight and batch stability of the polymer.
Another object of the present invention is to provide a method for preparing the A-D-A type polymer containing metal element in the main chain.
The invention further aims to provide application of the A-D-A type polymer with the main chain containing the metal element in the field of organic semiconductor devices.
In order to achieve the purpose, the invention adopts the following technical scheme.
A-D-A type polymer with a main chain containing metal elements has a chemical structural formula which satisfies the following general formula:
Figure BDA0001717428850000021
wherein n is the number of repeating units, and n is a positive integer of 2-1000;
a is an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 2 to 60 carbon atoms;
m is selected, identically or differently on each occurrence, from a group containing a metal atom, preferably a mercury atom or a platinum group Pt with a phosphorus ligand (P (R)1)3)2；
R1Is a linear alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms or a heteroaromatic organic group having 3 to 60 carbon atoms, two or more groups R1May be linked to each other and may form a ring;
d is selected from aromatic organic groups with 6-80 carbon atoms or heteroaromatic organic groups with 3-100 carbon atoms, which are the same or different at each occurrence.
Further, the a group is preferably a halogenated, deuterated, alkyl-substituted derivative of the following structure or of the following structure:
Figure BDA0001717428850000022
Figure BDA0001717428850000031
Figure BDA0001717428850000041
wherein X is selected, identically or differently on each occurrence, from C-R2A group or an N atom;
R2each occurrence being the same or different and selected from H, D, F, Cl, CN, NO2、C(＝O)R3,Si(R3)3,N(R3)2,P(＝O)(R3)2,P(＝S)(R3)2,OR3,SR3,S(＝O)R3,S(＝O)2R3A linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms or a heteroaromatic organic group having 3 to 60 carbon atoms, wherein R is2One or more-CH groups may contain2The radical may be represented by-R3C＝CR3-,-C≡C-,Si(R3)2,C＝O,C＝NR3,-C(＝O)O-,-C(＝O)NR3-,NR3,P(＝O)(R3),P(＝S)(R3) O, S, S (═ O) or SO2Replacing; two or more radicals R2May be linked to each other and may form a ring;
R3each occurrence being the same or different and selected from a straight chain alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms, or a heteroaromatic organic group having 3 to 60 carbon atoms; two or more radicals R3May be linked to each other and may form a ring.
Furthermore, the electron donor units D are preferably one or more of the following structures or halogenated, deuterated, alkyl, alkoxy, alkylthio-substituted derivatives of the following structures, respectively:
Figure BDA0001717428850000051
wherein K is C (R)4)2,NR4,BR4,C(R4)2O,Si(R4)2,Ge(R4)2,R4C＝CR4,C(R4)2C(R4)2,C＝O,C＝NR4,C(＝O)O,C(＝O)NR4,P(＝O)(R4),P(＝S)(R4) O, S, Se, Te, S (═ O) or SO2(ii) a Z is as defined above.
Wherein R is4Each occurrence identically or differently selected from a straight-chain alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms or a heteroaromatic organic group having 3 to 60 carbon atoms, wherein R is4May contain one or more-CHs2The radical may be represented by-R5C＝CR5-,-C≡C-,Si(R5)2,C＝O,C＝NR5,-C(＝O)O-,-C(＝O)NR5-,NR5,P(＝O)(R5),P(＝S)(R5) O, S, S (═ O) or SO2Replacing; r5Each occurrence being the same or different and selected from a straight chain alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms, or a heteroaromatic organic group having 3 to 60 carbon atoms; two or more radicals R4、R5May be linked to each other and may form a ring.
Further, in the A-D-A type polymer having a main chain containing a metal element, the molecular dipoles of the two A units in each A-D-A repeating unit are oriented oppositely.
The invention also provides a preparation method of the A-D-A type polymer with the main chain containing the metal element, which comprises the following steps:
(1) performing Stille coupling on the D unit containing the dialkyl tin functional group and dibromo or iodo Ar to obtain dibromo or iodo A-D-A unit;
(2) reacting dibromo or iodo A-D-A units with trialkyl acetylene silicon in a solvent to obtain di (trialkyl silicon) acetylene end group A-D-A units; reacting the A-D-A unit of the di (trialkylsilyl) acetylene end group with an alkali solution to obtain an A-D-A unit of a diacetylene end group;
(3) and reacting the A-D-A unit of the diacetylene end group with a metal compound to obtain the A-D-A type polymer with the main chain containing metal elements.
Furthermore, the molar ratio of the D containing the dialkyl tin functional group to the A unit of the dibromo or iodo group is 1: 2-1: 4, the reaction solvent includes but is not limited to toluene, xylene, chlorobenzene, tetrahydrofuran, and the like, the reaction catalyst includes but is not limited to tetrakis (triphenylphosphine) palladium, palladium acetate/tri-tert-butylphosphine, tris (dibenzylideneacetone) dipalladium/tris (o-tolylphosphine), and the like, and the reaction temperature is 20-140 ℃.
Further, the molar ratio of the dibromo or iodo a-D-a unit to the trialkylethylene silicon in the step (2) is 1:2 to 1:10, the reaction solvent includes, but is not limited to, diisopropylamine, toluene, xylene, chlorobenzene, tetrahydrofuran, water, methanol, ethanol, isopropanol, and the like, and the reaction temperature is 0 to 150 ℃.
Further, the method for synthesizing a-D-a type polymer with a main chain containing a metal element in step (3) above comprises the following steps:
(a) under the protection of inert gas, dissolving the A-D-A monomer with the diacetylene end group in an organic solvent, then adding a metal compound, and reacting for 0.1-36 hours at the temperature of 0-100 ℃;
(b) adding an alkaline solution, preferably a solution of hydroxide of alkali metal or alkaline earth metal, and continuously reacting for 0.1-36 hours;
(c) and after the reaction is finished, purifying the obtained precipitate to obtain the target product.
Further, the organic solvent in the step (a) includes, but is not limited to, at least one of ethanol, isopropanol, glycerol, acetic acid, acetone, carbon disulfide, diethyl ether, ethyl acetate, pyridine, tetrahydrofuran, methyl tetrahydrofuran, chlorobenzene, and dichlorobenzene.
Further, the diacetylene-terminated A-D-A monomers and metal compound monomers described in step (a) are used in amounts such that the total molar amount of diacetylene-functional group-containing monomers and the total molar amount of metal compound monomers are equal.
Further, the amount of the alkali used in the step (b) is 0.1-100 times of the total molar amount of the reaction monomers.
Further, the purification in step (c) means that the obtained precipitate is dried without filtration to obtain a crude product, the crude product is dissolved by a solvent and then filtered again, concentrated and precipitated in a methanol solution after concentration, filtered and dried to obtain the target product.
An electronic device selected from the group consisting of: organic thin film transistors (OFET), Organic Light Emitting Transistors (OLET), Organic Solar Cells (OSC), Organic Photodiodes (OPD), Organic Phototransistors (OPT), organic light emitting electrochemical cells (OLEC), organic electroluminescent diode devices (OLED), said electronic device comprising at least one of the above-mentioned a-D-a type polymers having a main chain containing a metal element.
Further, the A-D-A type polymer with the main chain containing the metal element is used for preparing an electronic device, and the A-D-A type polymer with the main chain containing the metal element is dissolved in an organic solvent and then is subjected to spin coating, ink-jet printing or printing to form a film.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) the introduction of metal atoms can provide potential supramolecular action, inducing molecular aggregation.
(2) The A-D-A regular structure is beneficial to the accumulation of polymer molecules, the mobility is further improved, and the absorption spectrum is red-shifted, and in addition, the regular structure is beneficial to the improvement of the molecular weight and batch stability of the polymer.
Drawings
Fig. 1 is a graph of current density-voltage characteristics of an organic/polymer photodetector device based on polymer P1.
FIG. 2 is a graph of the spectral responsivity characteristics of an organic/polymer photodetector device based on polymer P1 under a-0.1V bias.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
Preparation of Compound D1
(1) Preparation of Compound 1
Dithienocyclopentadiene (1.78g, 10mmol), sodium tert-butoxide (2.88g, 30mmol) and bromo-n-hexadecane (6.67g, 22mmol) were added to 100mL of tetrahydrofuran under nitrogen atmosphere and ice-bath, and the reaction was stirred for 24 hours. The tetrahydrofuran was spin-dried under reduced pressure, extracted with dichloromethane, washed 3 times with saturated aqueous sodium chloride solution, and the dichloromethane was spin-dried. The crude product is purified by column chromatography by using petroleum ether as eluent to obtain a white solid product with the yield of 90 percent.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound D1
Under the protection of nitrogen, compound 1(3.14g, 5mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, cooled to-5 ℃, and n-butyllithium (8mL, 20mmol) was added dropwise, and stirred at-5 ℃ for 2 hours. A tetrahydrofuran solution of trimethyltin chloride (45mL, 45mmol) was injected, and the reaction was allowed to spontaneously warm to room temperature for 12 hours. After tetrahydrofuran was distilled off under reduced pressure, the product was extracted with dichloromethane, washed 3 times with deionized water, and dichloromethane was spin-dried. Recrystallization from isopropanol afforded the product as a white solid in 87% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
The chemical reaction equations for the synthesis of compounds 1 and D1 are shown below:
Figure BDA0001717428850000081
example 2
Preparation of Compound D2
(1) Preparation of Compound 2
Under nitrogen, 3 '-dibromo 2, 2' -bithiophene (3.24g, 10mmol), sodium tert-butoxide (2.40g, 25mmol) 2-octyldodecylamine (3.57g, 12mmol), tris (dibenzylideneacetone) dipalladium (0.46g, 0.5mmol), and 2,2 '-bis- (diphenylphosphino) -1, 1' -binaphthyl (0.62g, 1mmol) were added to 100mL of anhydrous toluene. Heating to 100 deg.C for reaction for 12 hr, washing with saturated sodium chloride water solution for 3 times, spin-drying the solvent in organic layer, and purifying the crude product by column chromatography with petroleum ether as eluent to obtain colorless oily product with a yield of 70%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound D2
The reaction and purification of compound D2 were carried out in analogy to compound D1 to give the product as a pale yellow oil in 84% yield.1HNMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
The chemical reaction equations for the synthesis of compounds 2 and D2 are shown below:
Figure BDA0001717428850000091
example 3
Preparation of Compound A1
Under the protection of nitrogen, 2, 5-dibromo-3, 4-diaminopyridine (2.67g, 10mmol) and selenium dioxide (2.78g, 15mmol) were dissolved in 50mL of ethanol, and the mixture was heated to reflux for 12 hours. After cooling, recrystallization from chloroform gave the product as a bright yellow solid in 70% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
The chemical reaction equation for synthesizing compound a1 is shown below:
Figure BDA0001717428850000092
example 4
Preparation of Compound A2
Under the protection of nitrogen, 2, 5-dibromo-3, 4-diaminopyridine (2.67g, 10mmol) was dissolved in 30mL of pyridine, cooled to 0 ℃, added with thionyl chloride (1.79g, 15mmol), and naturally warmed to room temperature and stirred for 12 hours. The product was extracted with dichloromethane and after drying the organic layer solvent under reduced pressure, the crude product was purified by distillation with petroleum ether: ethyl acetate 4: column chromatography purification of 1(v/v) as eluent gave the product as a white solid in 51% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
The chemical reaction equation for synthesizing compound a2 is shown below:
Figure BDA0001717428850000101
example 5
Preparation of Compound A3
(1) Preparation of Compound 3
Compound A1(3.42g, 10mmol) was dissolved in 50mL fuming sulfuric acid under nitrogen, 1mL fuming nitric acid was added, and the mixture was stirred at room temperature for 6 hours. The reaction solution was slowly poured into 500mL of ice water, filtered, and the residue was recrystallized with chloroform to a yellow solid product with a yield of 75%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound 4
Compound 3(3.87g, 10mmol) and iron powder (1.12g, 20mmol) were added to 100mL of ethanol, and 5mL of concentrated hydrochloric acid was added thereto, followed by stirring and reacting for 6 hours. The product was extracted with dichloromethane and after 3 washes with deionized water, the organic layer solvent was spin dried to give the product as a brown solid with 90% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound A3
Compound 4(3.57g, 10mmol) was dissolved in 100mL of dichloromethane containing a small amount of polyvinyl alcohol, 5mL of hydrochloric acid was stirred at 0 ℃ for 1 hour under ice bath, and nitrous acid was addedSodium (1.38g, 20mmol) was stirred for an additional 2 hours and finally cuprous chloride was added and the reaction stirred for 12 hours. The product was extracted with dichloromethane and after 3 washes with deionized water, the organic layer solvent was spin dried and the crude product was purified with petroleum ether: ethyl acetate 4: 1 (volume ratio) is used as eluent for column chromatography purification, and bright yellow solid products are obtained with the yield of 53 percent.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
The chemical reaction equations for the synthesis of compounds 3,4 and a3 are shown below:
Figure BDA0001717428850000102
example 6
Synthesis of Polymer P1
(1) Preparation of Compound 5
Under a nitrogen atmosphere, compound A1(7.52g, 22mmol), compound D1(9.53g, 10mmol), and tetrakis (triphenylphosphine) palladium (0.58g, 0.5mmol) were dissolved in 200mL of anhydrous toluene, and the mixture was heated to 100 ℃ for reaction for 8 hours. After spin-drying of the toluene, the crude product was purified with petroleum ether: ethyl acetate ═ 1: column chromatography purification of 1(v/v) as eluent gave the solid product in 57% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound 6
In a 500mL two-necked round-bottomed flask, under a nitrogen atmosphere, Compound 5(22.98g, 20mmol), bis (triphenylphosphine) palladium dichloride (0.475g, 0.68mmol), cuprous iodide (0.052g, 0.28mmol), 200mL degassed toluene, and 60mL degassed diisopropylamine were added all at once, and the solids were dissolved and mixed well by stirring. Under argon atmosphere, a solution of trimethylethynylsilicon (4.32g,44.0mmol) in diisopropylamine (30mL) was added dropwise at room temperature. After the dropwise addition, the temperature of the reaction solution is raised to 70 ℃, and the reaction is carried out for 6 hours under the protection of argon. Monitoring the reaction degree by using thin-layer chromatography, cooling the reaction liquid to room temperature after the reaction is finished, and filtering to remove impurities such as solid salt and the like. The crude product is subjected to column chromatography (silica gel column, eluting with petroleum ether)Separating and purifying, further recrystallizing with methanol to obtain white solid, filtering, and vacuum drying to obtain 70% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound 7
To a solution of compound 6(14.2g, 12.0mmol) in tetrahydrofuran (100mL) under a nitrogen atmosphere was added 15mL of a 20 wt% aqueous solution of potassium hydroxide, followed by 50mL of methanol to dilute the reaction. The mixture is evenly stirred and reacted for 1 hour under the condition of argon protection and normal temperature. Monitoring the reaction degree by thin-layer chromatography, pouring the reaction liquid into ice water after the reaction is finished, extracting by dichloromethane, washing an oil layer by water and a saturated sodium chloride aqueous solution respectively, and concentrating to obtain a crude product. The crude product was isolated and purified by column chromatography (silica gel column, eluent petroleum ether) and further recrystallized from methanol to give a white solid, which was filtered and vacuum dried at a yield of 81%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Preparation of Polymer P1
Under the protection of nitrogen, dissolving compound 7(1039.3mg, 1mmol) in 15mL ethyl acetate, adding mercury dichloride (272mg, 1mmol), reacting for 10 minutes, dropwise adding 10mL 0.1M sodium hydroxide methanol solution, reacting for 10 minutes, filtering to obtain a crude product, dissolving the crude product in tetrahydrofuran, filtering through a 0.45-micron polytetrafluoroethylene organic filter membrane, concentrating, precipitating the concentrated solution in methanol to obtain a filamentous polymer, and finally drying the filter cake obtained by suction filtration in a vacuum oven at 45 ℃ for 24 hours to obtain 984mg of dark green flocculent polymer solid P1, wherein the yield is 68%.
The chemical reaction equation is as follows:
Figure BDA0001717428850000121
example 7
Preparation of Polymer P2
(1) Preparation of Compound 8
The reaction and purification of compound 8 was carried out in analogy to compound 5 to give the product as a solid in 62% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound 9
The reaction and purification of compound 9 was carried out in analogy to compound 6 to give the product as a solid in 62% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound 10
The reaction and purification of compound 10 was carried out in analogy to compound 7 to give the solid product in 62% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Preparation of Polymer P2
The reaction and purification method of the polymer P2 were similar to those of the polymer P1, and a black fibrous polymer was obtained.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
The chemical reaction equation is as follows:
Figure BDA0001717428850000131
example 8
Preparation of Polymer P3
(1) Preparation of Compound 11
The reaction and purification of compound 11 was carried out in analogy to compound 5 to give the solid product in 53% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound 12
The reaction and purification of compound 12 was carried out in analogy to compound 6 to give the solid product in 53% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound 13
The reaction and purification of compound 13 was carried out in analogy to compound 7 to give the solid product in 53% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Preparation of Polymer P3
The reaction and purification method of the polymer P3 were similar to those of the polymer P1, and a black fibrous polymer was obtained.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
The chemical reaction equation is as follows:
Figure BDA0001717428850000141
example 9
Preparation of Polymer P4
(1) Preparation of Compound 14
The reaction and purification of compound 14 was carried out in analogy to compound 5 to give the solid product in 69% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Preparation of Compound 15
The reaction and purification of compound 15 was carried out in analogy to compound 6 to give the solid product in 69% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound 16
The reaction and purification of compound 16 was carried out analogously to compound 7 to give the product as a solid in 69% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Preparation of Polymer P4
The reaction and purification method of the polymer P4 were similar to those of the polymer P1, and a black fibrous polymer was obtained.1H NMR and elemental analysis results showed that the obtained compoundIs a target product. The reaction equation is as follows:
Figure BDA0001717428850000161
example 10
Preparation of Polymer photodetector
Indium Tin Oxide (ITO) glass with the square resistance of 15 omega, which is prepared in advance, is taken, and ultrasonic cleaning and plasma treatment are sequentially carried out on the Indium Tin Oxide (ITO) glass for 10 minutes by using acetone, a detergent, deionized water and isopropanol. A film of polyethoxythiophene (PEDOT: PSS) doped with polystyrene sulfonic acid was spin-coated on ITO to a thickness of 40 nm. PEDOT PSS films were dried in a vacuum oven at 80 ℃ for 8 hours. Then the polymers P1 and PC were mixed in a mass ratio of 1:171A solution of BM in o-dichlorobenzene (1 wt.%) was spin coated on the surface of PEDOT: PSS film to a thickness of 100 nm. Then, a PFN-Br film with a thickness of about 5nm is spin-coated on the active layer. Finally, a metal Al layer with the thickness of 100nm is evaporated, and the structure of the device is ITO/PEDOT (indium tin oxide)/PSS/P1 (Polybutylece oxide)/PC (polycarbonate)71BM/PFN-Br/Al。
Fig. 1 is a current density-voltage characteristic diagram of an organic/polymer photodetector device based on polymer P1.
The device has good light detection characteristics, and the current density under the same voltage is improved under the illumination condition. FIG. 2 is a graph of the spectral responsivity characteristics of an organic/polymer photodetector device based on the polymer P1 under a bias voltage of-0.1V, and it can be seen that the device has a photoelectric response at 300-1000 nm.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (11)

1. A-D-A type polymer with a main chain containing metal elements is characterized in that the structural formula is shown as P1-P4:
Figure FDA0003500018250000011
Figure FDA0003500018250000021
Figure FDA0003500018250000031
Figure FDA0003500018250000041
wherein n is the number of repeating units, and n is 2 to 1000.
2. The A-D-A type polymer containing metal element in main chain according to claim 1, wherein the molecular dipoles of two A units in each A-D-A repeating unit are oriented oppositely.
3. A method for preparing the A-D-A type polymer with the main chain containing the metal element as set forth in any one of claims 1 to 2, which is characterized by comprising the following steps:
(1) performing Stille coupling on the D unit containing the dialkyl tin functional group and the dibromo or iodo A unit to obtain the dibromo or iodo A-D-A unit;
(2) reacting dibromo or iodo A-D-A units with trialkyl acetylene silicon in a solvent to obtain di (trialkyl silicon) acetylene end group A-D-A units; reacting the A-D-A unit of the di (trialkylsilyl) acetylene end group with an alkali solution to obtain an A-D-A unit of a diacetylene end group;
(3) and reacting the A-D-A unit of the diacetylene end group with a metal compound to obtain the A-D-A type polymer with the main chain containing metal elements.
4. The preparation method according to claim 3, wherein the molar ratio of the D containing the tin dialkyl functional group to the A unit of the dibromo or iodo group in the step (1) is 1:2 to 1: 4; the Stille coupling reaction solvent in the step (1) is toluene, xylene, chlorobenzene or tetrahydrofuran, and the reaction catalytic system is tetrakis (triphenylphosphine) palladium or a mixture of the tetrakis (triphenylphosphine) palladium and the tetrahydrofuran in a mass ratio of 1: 1-1: 3 palladium acetate: tri-tert-butylphosphine or 1: 1-1: 3 tris (dibenzylideneacetone) dipalladium: the reaction temperature of the tri (o-methyl phenylphosphine) is 20-140 ℃.
5. The method according to claim 3, wherein the molar ratio of the dibromo or iodo A-D-A unit to the trialkylethylene silicon in step (2) is 1:2 to 1:10, the reaction solvent is diisopropylamine, toluene, xylene, chlorobenzene, tetrahydrofuran, water, methanol, ethanol or isopropanol, and the reaction temperature is 0 to 150 ℃.
6. The preparation method according to claim 3, wherein the step (3) specifically comprises the following processes:
(a) under the protection of inert gas, dissolving the A-D-A monomer with the diacetylene end group in an organic solvent, then adding a metal compound, and reacting for 0.1-36 hours at the temperature of 0-100 ℃;
(b) adding an alkaline solution, adopting a solution of hydroxide of alkali metal or alkaline earth metal, and continuously reacting for 0.1-36 hours;
(c) and after the reaction is finished, purifying the obtained precipitate to obtain the target product.
7. The method for preparing A-D-A type polymers containing metal elements in the main chain according to claim 6, wherein: the organic solvent in the step (a) is at least one of ethanol, isopropanol, glycerol, acetic acid, acetone, carbon disulfide, diethyl ether, ethyl acetate, pyridine, tetrahydrofuran, methyltetrahydrofuran, chlorobenzene and dichlorobenzene.
8. The method for preparing A-D-A type polymers containing metal elements in the main chain according to claim 6, wherein: the amount of the A-D-A monomer with diacetylene end groups and the metal compound monomer in the step (a) is such that the total molar amount of the monomers containing diacetylene functional groups is equal to the total molar amount of the metal compound monomer; the solute dosage of the alkaline solution in the step (b) is 0.1-100 times of the molar total amount of the A-D-A monomer of the diacetylene end group.
9. The method for preparing A-D-A type polymers containing metal elements in the main chain according to claim 6, wherein: and (c) purifying, namely filtering and drying the obtained precipitate to obtain a crude product, dissolving the crude product with a solvent, filtering again, concentrating, precipitating in a methanol solution after concentrating, filtering, and drying to obtain the target product.
10. Use of a polymer of type a-D-a with a main chain containing a metal element according to any one of claims 1 to 2 for the manufacture of an electronic device, characterized in that: the electronic device comprises an organic thin film transistor OFET, an organic light emitting transistor OLET, an organic solar cell OSC, an organic photodiode OPD, an organic phototransistor OPT, an organic light emitting electrochemical cell OLEC and an organic electroluminescent diode device OLED.
11. Use of a class of a-D-a polymers having a main chain containing a metal element according to any one of claims 1 to 2 for the preparation of an electronic device according to claim 10, wherein: the A-D-A type polymer with the main chain containing the metal element is dissolved in an organic solvent and then is subjected to spin coating, ink-jet printing or printing to form a film.
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