CN115322338B - Organic semiconductor material containing thiophene pyridine isoindigo structure, and preparation method and application thereof - Google Patents

Organic semiconductor material containing thiophene pyridine isoindigo structure, and preparation method and application thereof Download PDF

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CN115322338B
CN115322338B CN202210974753.7A CN202210974753A CN115322338B CN 115322338 B CN115322338 B CN 115322338B CN 202210974753 A CN202210974753 A CN 202210974753A CN 115322338 B CN115322338 B CN 115322338B
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isoindigo
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董方亮
王明
唐正
马在飞
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Donghua University
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Abstract

The invention relates to an organic semiconductor material containing thiophene pyridine isoindigo structure, which has a structure shown in formula I:in the formula I, n is a natural number of 1-2000; pi is an aromatic conjugated unit; r, R' includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, triacontyl, isopropylisobutyl, 2-ethylhexyl, 2-butylhexyl and the like, respectively. The polymer containing the thiophene pyridine isoindigo structure has a plurality of alkyl branched chains, has higher carrier mobility, good solubility and thermal stability compared with the prior art, is beneficial to carrier transmission, improves the performance of devices and the like, and can be applied to the fields of organic semiconductor films, organic photovoltaic cell devices, organic field effect transistor devices and the like. In addition, the invention also provides a preparation method of the organic semiconductor material containing the thiophene pyridine isoindigo structure.

Description

Organic semiconductor material containing thiophene pyridine isoindigo structure, and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic high polymer semiconductor materials, in particular to an organic semiconductor material containing a thiophene pyridine isoindigo structure, and a preparation method and application thereof.
Background
Organic semiconductors have been used in optoelectronic devices such as Organic Light Emitting Diodes (OLEDs), organic Field Effect Transistors (OFETs), and Organic Solar Cells (OSCs) for the last decades. OSCs have attracted considerable attention due to their potential for simple preparation, lightweight, and large area roll-to-roll processing (angel. Chem. Int. Ed.2008,47,58-77; nat. Photon.2012,6,153-161; acc. Chem. Res.2012,45,723-733;Energy Environ.Sci.2015,8,1160-1189;Acta Polym.Sin.2019,50,988-1046.). Recently, bulk heterojunction OSCs using conjugated polymers as electron donor (D) materials and small molecule electron acceptors (a) as acceptor materials have made tremendous progress, and their energy conversion efficiency (PCE) has exceeded 20% (joule.2022, 6, 171-184.). OFETs have received great attention because of their conversion of ion signals to electronic signals at low electrochemical potentials, which has greatly facilitated the development of electronic technology (angel.chem.int.ed.2020, 59,14449-14457; adv.mate.2018, 30,1705745; angel.chem.int.ed.2021, 60, 24198-24205.).
Currently, only a few OSCs based on the D-a structure can achieve an energy conversion efficiency of 15%, and the donors they use include PM6, PTQ10, P2F-EHp, D16 and W1 (sci.china.chem.2019, 62,746-52; sci.bull.2019,64,1573-6; nat.Commun.2018,9, 743.). The main factors limiting the energy conversion efficiency of OSCs are the narrow absorption spectrum, low molar absorption coefficient, etc. of the existing polymer systems. There are currently also only a few OFETs based on organic semiconducting polymers with carrier mobilities up to 1cm 2 V -1 s -1 These polymers include P-BN-IID, PDTzTI, PBTI and P (BTI-BTI 2) (Angew.chem.Int.Ed.2016, 55,5313-5317; adv.Mater.2018,30,1705745; angew.chem.Int.Ed.2019,58, 11893-11902.). The main factors limiting the mobility of OFETs carriers are that the existing polymer system has narrower absorption spectrum, wider energy level band gap and the like.
Chinese patent CN103865041a discloses a conjugated polymer containing isoindigo-dibenzothiophene and its preparation method and application, the polymer is formed by combining dibenzothiophene and dibenzothiophene as the structural units of the conjugated polymer and isoindigo units, so as to improve the solubility of the conjugated polymer, but the isoindigo introduced in the dibenzothiophene and dibenzothiophene structure can only twist the phenomenon that the pi-pi non-bonding strength between conjugated polymer chains is stronger than the chemical bonding strength in the molecule to a certain extent, and the method has limited and unstable improvement of the solubility.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an organic semiconductor material containing a thiophene pyridine isoindigo structure, a preparation method and application thereof, wherein the organic semiconductor material containing the thiophene pyridine isoindigo structure can overcome the problems of single structure, poor chemical adjustability and the like of a polymer non-fullerene system, and has higher mobility and adjustable energy level; the semiconductor material can be effectively matched with sunlight spectrum, so that the device can obtain higher carrier mobility, open-circuit voltage and short-circuit current density, and can be used as an active layer material in an organic photovoltaic cell device and an organic field effect transistor device.
The aim of the invention can be achieved by the following technical scheme:
an organic semiconductor material containing thiophene pyridine isoindigo structure, which has a structure shown in a formula I:
in the formula I, n is a natural number of 1-2000; pi is an aromatic conjugated unit; r, R' includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, triacontyl, isopropyl isobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl or 2-dodecyloctadecyl, respectively.
Further, pi is
In pi, R 1 Including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and decaMono-, dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, triacontyl-, isopropyl-isobutyl-, 2-ethylhexyl-, 2-butylhexyl-, 2-butyloctyl-, 2-hexyloctyl-, 2-hexyldecyl-, 2-hexyldodecyl-, 2-octyldecyl-, 2-octyldodecyl-, 2-octyltetradecyl-, 2-octylhexadecyl-, 2-decyldodecyl-, 2-decyltetradecyl-, 2-decylhexadecyl-, 2-dodecyltetradecyl-, 2-dodecylhexadecyl-, or 2-dodecyloctadecyl.
In pi, X 1 Hydrogen, fluorine, chlorine, bromine or iodine.
Further, the organic semiconductor material containing the thiophene pyridine isoindigo structure comprises:
a preparation method of an organic semiconductor material containing a thiophene pyridine isoindigo structure comprises the following steps:
s1, thienopyran-4, 6-dione and NH 2 R is mixed and subjected to addition reaction to obtain an intermediate a with a structure shown in a formula II;
s2, mixing the intermediate a with the structure shown in the formula II with thienopyrrole-4-alkyl-5, 6-dione, and performing condensation reaction to obtain an intermediate b with the structure shown in the formula III;
S3, carrying out bromination reaction on the intermediate b with the structure shown in the formula III and N-bromosuccinimide (NBS) in an N, N-Dimethylformamide (DMF) solvent to obtain an intermediate c with the structure shown in the formula IV;
s4, mixing the intermediate c with the structure shown in the formula IV with H-pi-H, and performing Stille coupling reaction under the catalysis of a palladium catalyst to obtain an organic semiconductor material with a thiophene pyridine isoindigo structure shown in the formula I;
further, the molar ratio of thienopyran-4, 6-dione to NH2-R described in step S1 is preferably 1:1.0 to 1.1:0.30 to 0.35, more preferably 1:1:0.33.
further, the addition reaction described in step S1 is carried out in an o-xylene solvent, and the ratio of the amount of thienopyran-4, 6-dione to the amount of o-xylene is preferably 3.8mmol:10 to 15mL, more preferably 3.8mmol:10mL.
Further, the ortho-xylene is preferably anhydrous ortho-xylene.
Further, the temperature of the addition reaction in step S1 is preferably 160 to 180 ℃, more preferably 170 ℃; the reaction time is preferably 10 to 14 hours, more preferably 12 hours.
Further, after the completion of the addition reaction described in step S1, the reaction solution was extracted with water and methylene chloride, and then the lower organic phase was taken out, dried over anhydrous magnesium sulfate and filtered, and the solvent was removed by a rotary evaporator to obtain a crude product, which was purified by column chromatography to obtain intermediate a having the structure represented by formula ii as a reddish brown liquid.
Further, the molar ratio of intermediate a to thienopyrrole-4-alkyl-5, 6-dione described in step S2 is preferably 1:1.0 to 1.2, more preferably 1:1.1.
further, the condensation reaction described in step S2 is carried out in the presence of a solvent, preferably a mixed solution of toluene and acetic acid.
Further, the intermediate a and thienopyrrole-4-alkyl-5, 6-dione described in step S2 are added to a mixed solution of toluene and acetic acid, and the reaction is stirred at 115 ℃.
Further, the concentration of the mixed solution in the step S2 is preferably 0.2 to 0.3mol/L, more preferably 0.25mol/L, and the volume ratio of toluene to acetic acid is preferably 2:1.
further, the toluene is preferably anhydrous toluene.
Further, the time of the condensation reaction in step S2 is preferably 10 to 14 hours, more preferably 12 hours.
Further, after the condensation reaction described in step S2 is completed, the reaction solution is poured into water to quench, extracted with water and methylene chloride, then the lower organic phase is taken out, dried using anhydrous magnesium sulfate and filtered, the solvent is removed by a rotary evaporator to obtain a crude product, and the crude product is purified by column chromatography to obtain intermediate b having the structure shown in formula iii, wherein intermediate b is a blackish brown solid.
Further, the molar ratio of intermediate b to N-bromosuccinimide (NBS) described in step S3 is preferably 1:2.1 to 2.3, more preferably 1:2.2.
further, the concentration of the intermediate b in the N, N-Dimethylformamide (DMF) solvent in the step S3 is preferably 0.1 to 0.2mol/L, more preferably 0.15mol/L.
Further, the temperature of the bromination reaction in step S3 is preferably room temperature, and the reaction time is preferably 8 to 12 hours, more preferably 10 hours.
Further, the bromination reaction described in step S3 is preferably carried out under a dark condition, and the effect is to avoid side reactions of N-bromosuccinimide (NBS) under light.
Further, the addition reaction, condensation reaction and bromination reaction are preferably carried out under stirring conditions and a nitrogen atmosphere, and the stirring speed is preferably 450rpm.
Further, after the bromination reaction described in step S3 is completed, the reaction solution is poured into water to quench, extracted with water and methylene chloride, then the lower organic phase is taken out, dried using anhydrous magnesium sulfate and filtered, the solvent is removed by a rotary evaporator to obtain a crude product, and the crude product is purified by column chromatography to obtain an intermediate c having a structure represented by formula iv, wherein the intermediate c is a deep blue solid.
Further, the molar ratio of intermediate c to H-pi-H in step S4 is preferably 1:1.0 to 1.1, more preferably 1:1.01 to 1.05.
Further, the palladium catalyst described in step S4 is preferably tetrakis (triphenylphosphine) palladium.
Further, the molar ratio of the intermediate c to the palladium catalyst in step S4 is preferably 1:0.04 to 0.06, more preferably 1:0.05.
further, the Stille coupling reaction described in step S4 is preferably carried out in the presence of an organic solvent, preferably o-xylene.
Further, the ratio of the amount of the intermediate c to the amount of o-xylene in step S4 is preferably 1mmol:50 to 150mL, more preferably 1mmol:120mL.
Further, in step S4, the intermediate c, H-pi-H and the palladium catalyst are mixed, and the nitrogen is replaced by vacuum pumping three times, and then o-xylene is added to remove the interference of water and oxygen in the air.
Further, the temperature of the Stille coupling reaction in step S4 is preferably 120 to 160 ℃, more preferably 140 ℃, and the reaction time is preferably 36 to 72 hours, more preferably 48 hours.
Further, the Stille coupling reaction described in step S4 is preferably carried out in a nitrogen atmosphere.
Further, after the Stille coupling reaction in the step S4 is completed, cooling the obtained reaction system to room temperature, then dripping the reaction system into methanol to precipitate out precipitate, and filtering to obtain a solid material, namely a crude product; the crude product is sequentially purified by methanol, normal hexane, methylene dichloride and chloroform, chloroform phase concentrate is dripped into the methanol for secondary precipitation, the obtained solid material is dried after filtration, and the organic semiconductor material with the thiophene pyridine isoindigo structure and the structure shown in the formula I is obtained, wherein the organic semiconductor material is a deep blue solid. .
Further, the dropping speed in the step S4 is preferably 0.4 to 0.6mL/min, more preferably 0.5mL/min.
The invention also provides an organic semiconductor film which is formed by the organic semiconductor polymer containing the thiophene pyridine isoindigo structure in the technical scheme or the solution of the organic semiconductor polymer containing the thiophene pyridine isoindigo structure prepared by the preparation method in the technical scheme.
The invention also provides an organic photovoltaic cell device, which comprises an electron donor material and an electron acceptor material, and is characterized in that the electron donor material comprises the organic semiconductor polymer containing the thiophene pyridine isoindigo structure in the technical scheme or the organic semiconductor polymer containing the thiophene pyridine isoindigo structure prepared by the preparation method in the technical scheme.
Further, the electron acceptor material includes Y6.
The invention also provides an organic field effect transistor device, and the active layer material comprises the organic semiconductor polymer containing the thiophene pyridine isoindigo structure in the technical scheme or the organic semiconductor polymer containing the thiophene pyridine isoindigo structure prepared by the preparation method in the technical scheme.
Compared with the prior art, the organic semiconductor material containing the thiophene pyridine isoindigo structure, and the preparation method and application thereof have the following advantages:
1. the main chain of the thiophene pyridine isoindigo fused ring structural unit has high planarity, and is simultaneously connected with different aromatic units for modification, thereby being beneficial to adjusting energy level and film morphology and promoting the transmission of charge carriers;
2. the organic semiconductor polymer provided by the invention has a plurality of alkyl branched chains, so that the polymer has good solubility, and a polymer solution can form a film on a substrate in a drop coating or spin coating mode in the preparation of a device, thereby being beneficial to optimizing the appearance of the film and improving the performance of the device;
3. the organic semiconductor polymer containing the thiophene pyridine isoindigo structure provided by the invention has good thermal stability, can be prepared in a laboratory in a high-efficiency and economic way, has good response to sunlight, enables a device to obtain higher carrier mobility, open-circuit voltage and short-circuit current density, and can be used as an active layer component of an organic photovoltaic cell device and an active layer component of an organic field effect transistor device.
Drawings
FIG. 1 is a thermogravimetric and differential scanning calorimetry plot of polymer F1 in example 1 of the present invention;
FIG. 2 is a cyclic voltammogram and absorption spectrum of the polymer F1 in example 1 of the present invention;
FIG. 3 is a thermogravimetric and differential scanning calorimetry plot of polymer F2 in example 2 of the present invention;
FIG. 4 is a cyclic voltammogram and absorption spectrum of the polymer F2 in example 2 of the present invention;
FIG. 5 is a thermogravimetric and differential scanning calorimetry plot of polymer F3 in example 3 of the present invention;
FIG. 6 is a cyclic voltammogram and absorption spectrum of polymer F3 in example 3 of the present invention;
FIG. 7 is a thermogravimetric and differential scanning calorimetry plot of polymer F4 in example 4 of the present invention;
FIG. 8 is a cyclic voltammogram and absorption spectrum of polymer F4 in example 4 of the present invention;
FIG. 9 is a thermogravimetric and differential scanning calorimetry plot of polymer F5 in example 5 of the present invention;
FIG. 10 is a cyclic voltammogram and absorption spectrum of polymer F5 in example 5 of the present invention;
FIG. 11 is a thermogravimetric and differential scanning calorimetry plot of polymer F6 in example 6 of the present invention;
FIG. 12 is a cyclic voltammogram and absorption spectrum of polymer F6 in example 6 of the present invention;
FIG. 13 is a thermogravimetric and differential scanning calorimetry plot of polymer F7 in example 7 of the present invention;
FIG. 14 is a cyclic voltammogram and absorption spectrum of polymer F7 in example 7 of the present application;
FIG. 15 is a thermogravimetric and differential scanning calorimetry plot of polymer F8 in example 8 of the present application;
FIG. 16 is a cyclic voltammogram and absorption spectrum of polymer F8 in example 8 of the present application;
fig. 17 is a graph showing the current-voltage curve of the organic solar cell device prepared by using the polymer F4 as an electron donor material in example 4 of the present application.
Fig. 18 is a graph showing the output and transfer of an organic field effect transistor device prepared by using the polymer F1 as an active layer material in example 1 of the present application.
Detailed Description
The application will now be described in detail with reference to the drawings and specific examples.
In the application, the organic semiconductor material containing the thiophene pyridine isoindigo structure takes thiophene pyridine dione bithiophene pyrrole dione as a core unit and contains an exchangeable aromatic unit, so that electrons and holes can be transmitted.
The invention combines thienopyran-4, 6-dione and NH 2 R and 4-Dimethylaminopyridine (DMAP) are mixed and subjected to addition reaction in an o-xylene solvent to obtain an intermediate a with a structure shown in a formula II. In the present invention, thienopyran-4, 6-dione and NH 2 The molar ratio of R, DMAP is preferably 1:1.0 to 1.1:0.30 to 0.35, more preferably 1:1:0.33. in the present invention, the ratio of the amount of thienopyran-4, 6-dione to o-xylene is preferably 3.8mmol:10 to 15mL, more preferably 3.8mmol:10mL. In the present invention, the temperature of the addition reaction is preferably 160 to 180 ℃, more preferably 170 ℃; the time of the addition reaction is preferably 10 to 14 hours, more preferably 12 hours. The addition reaction is preferably carried out under stirring conditions, preferably at a stirring speed of 450rpm; in the present invention, the addition reaction is preferably performed under a nitrogen atmosphere; the ortho-xylene is preferably anhydrous ortho-xylene.
After the addition reaction is completed, the reaction solution is preferably extracted by water and methylene dichloride, then the lower organic phase is taken out, dried by anhydrous magnesium sulfate and filtered, and the solvent is removed by a rotary evaporator to obtain a crude product; the crude product is purified by column chromatography to obtain an intermediate a with a structure shown in a formula II. In the invention, the intermediate a with the structure shown in the formula II is reddish brown liquid.
In a specific embodiment of the present invention, the addition reaction has the following reaction formula:
after obtaining an intermediate a with a structure shown in a formula II, the invention mixes the intermediate a with the structure shown in the formula II with thienopyrrole-4-alkyl-5, 6-dione, and carries out condensation reaction in a mixed solvent of toluene and acetic acid to obtain an intermediate b with the structure shown in a formula III.
In the present invention, the molar ratio of the intermediate a having the structure represented by formula II to the thienopyrrole-4-alkyl-5, 6-dione is preferably 1:1.0 to 1.2, more preferably 1:1.1. in the present invention, the condensation reaction is carried out in the presence of a solvent, preferably a mixed solution of toluene and acetic acid. In the invention, the intermediate a and thienopyrrole-4-alkyl-5, 6-dione are added into a mixed solution of toluene and acetic acid, and the mixture is stirred and reacted at 115 ℃. In the present invention, the concentration of the mixed solution is preferably 0.2 to 0.3mol/L, more preferably 0.25mol/L; the volume ratio of toluene to acetic acid is preferably 2:1, a step of; in the present invention, the toluene is preferably anhydrous toluene.
In the present invention, the condensation reaction is preferably carried out at 115 ℃, and the time of the condensation reaction is preferably 10 to 14 hours, more preferably 12 hours; the condensation reaction is preferably carried out under stirring conditions, preferably at a stirring speed of 450rpm; the condensation reaction is preferably carried out under a nitrogen atmosphere.
After the condensation reaction is completed, the reaction solution is preferably poured into water for quenching, extracted by water and dichloromethane, then the lower organic phase is taken out, dried by anhydrous magnesium sulfate and filtered, and the solvent is removed by a rotary evaporator to obtain a crude product; purifying the crude product by column chromatography to obtain an intermediate b with a structure shown in a formula III. In the invention, the intermediate b with the structure shown in the formula III is a black brown solid.
In a specific embodiment of the present invention, the condensation reaction has the following reaction formula:
after obtaining an intermediate b with a structure shown in a formula III, the invention carries out bromination reaction on the intermediate b with the structure shown in the formula III and N-bromosuccinimide (NBS) in DMF solvent to obtain an intermediate c with the structure shown in a formula IV. In the present invention, the molar ratio of the intermediate b having the structure represented by formula iii to NBS is preferably 1:2.1 to 2.3, more preferably 1:2.2. in the present invention, the concentration of the DMF solution of the intermediate b having the structure represented by the formula III is preferably 0.1 to 0.2mol/L, more preferably 0.15mol/L; the temperature of the bromination reaction is preferably room temperature; the bromination reaction time is preferably 8 to 12 hours, more preferably 10 hours. The bromination reaction is preferably carried out under light-shielding conditions, and the purpose of the bromination reaction is to avoid side reactions of NBS under light. The bromination reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 450rpm; in the present invention, the bromination reaction is preferably carried out under a nitrogen atmosphere.
After the bromination reaction is finished, the reaction solution is preferably poured into water for quenching, extracted by water and dichloromethane, then the lower organic phase is taken out, dried by anhydrous magnesium sulfate and filtered, and the solvent is removed by a rotary evaporator to obtain a crude product; purifying the crude product by column chromatography to obtain an intermediate c with a structure shown in a formula IV. In the invention, the intermediate c with the structure shown in the formula IV is a dark blue solid.
In a specific embodiment of the present invention, the bromination reaction has the following reaction formula:
after obtaining an intermediate c with a structure shown in a formula IV, the invention mixes the intermediate c with the structure shown in the formula IV with H-pi-H, and carries out Stille polymerization under the catalysis of a palladium catalyst to obtain the organic semiconductor material with the structure shown in the formula I and containing thiophene pyridine isoindigo. In the present invention, the molar ratio of the intermediate c having the structure represented by formula IV to H-pi-H is preferably 1:1.0 to 1.1, more preferably 1:1.01 to 1.05. In the present invention, the palladium catalyst is preferably tetrakis (triphenylphosphine) palladium, and the molar ratio of the intermediate c having the structure shown in formula iv to the palladium catalyst is preferably 1:0.04 to 0.06, more preferably 1:0.05. in the present invention, the Stille polymerization is preferably carried out in the presence of an organic solvent, preferably o-xylene; the ratio of the amount of the intermediate c having the structure shown in formula IV to the amount of o-xylene is preferably 1mmol:50 to 150mL, more preferably 1mmol:120mL. In the invention, the intermediate c with the structure shown in the formula IV, H-pi-H and the palladium catalyst are preferably mixed, and the nitrogen is replaced by vacuumizing for three times, and then o-xylene is added to remove the interference of water and oxygen in the air.
In the present invention, the temperature of the Stille polymerization reaction is preferably 120 to 160 ℃, more preferably 140 ℃; the Stille polymerization reaction time is preferably 36-72 h, more preferably 48h; the Stille polymerization is preferably carried out under a nitrogen atmosphere.
After the Stille polymerization reaction is completed, the obtained reaction system is preferably cooled to room temperature, and then is dripped into methanol to precipitate out a precipitate, and a solid material, namely a crude product, is obtained after filtration; purifying the crude product by methanol, normal hexane, dichloromethane and chloroform in sequence; and (3) dropwise adding the chloroform phase concentrate into methanol for secondary precipitation, filtering, and drying the obtained solid material to obtain the organic semiconductor material with the thiophene pyridine isoindigo structure shown in the formula I. In the present invention, the dropping speed is preferably 0.4 to 0.6mL/min, more preferably 0.5mL/min. In the invention, the organic semiconductor material with the structure shown in the formula I and containing the thiophene pyridine isoindigo is a dark blue solid.
In a specific embodiment of the present invention, the Stille polymerization reaction has the following reaction formula:
the technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples of the present invention, thienopyran-4, 6-dione was synthesized artificially according to the procedure described in the literature (Francisco Manoni, stephen J.Connon, angew.Chem.Int.Ed.2014,53, 2628-2632); thienopyrrole-4-alkyl-5, 6-dione was synthesized according to procedures described in the literature (Mark s.chen, jean m.j. Friechet, chem. Mater.2013,25,20,4088-4096). Other chemical reagents are purchased by commercial companies, and are not further purified before use unless specified; the anhydrous toluene is prepared by distillation treatment of metallic sodium and benzophenone, and all reactions are carried out in nitrogen atmosphere in the process of preparing the organic semiconductor polymer containing the thiophene pyridine isoindigo structure; the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum are obtained through testing by a Bruce 400MHz nuclear magnetic resonance spectrometer in Switzerland; the ultraviolet spectrum of the polymer was measured by a PerkiElmer LAMBDA 950 spectrometer; the cyclic voltammogram is obtained by testing an electrochemical workstation of Shanghai Chenhua CHI730 e; thermal analysis was done by the race mer thermogravimetric and differential scanning calorimetric system test.
Example 1
Polymer F1 was prepared as follows:
(1) Synthesis of Compound 3: anhydride 1 (520 mg,3.1mmol,1.0 equiv.), 4-dimethylaminopyridine (DMAP, 156mg,1.3mmol,0.42 equiv.), o-xylene (10 mL) and a mini-stirrer were added to a dry 10-20mL microwave reaction tube under nitrogen atmosphere, after which octyldodecamine (1.4 g,4.0mmol,1.3 equiv.) was added dropwise to the mixture for more than 15min, and the mixture was stirred for 15min until the solid was completely dissolved. The microwave reaction tube was then placed in a microwave reactor (P max =400W), the reaction was carried out by microwaves at 240 ℃ for 2h. The above procedure was repeated three more times and the four reaction mixtures were collected together, o-xylene was removed by rotary evaporator and petroleum ether was used: dichloromethane (1:1) was used as eluent and purified by column chromatography on silica gel to give compound 3 (2.22 g,5.0mmol,40% yieldd) as a dark red oily viscous liquid. 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):7.50(d,J＝4Hz,1H),7.28(d,J＝4Hz,1H),4.11(s,2H),3.87(d,J＝8Hz,2H),1.86-1.81(m,J＝8Hz,1H),1.36-1.24(m,32H),0.89-0.85(m,5H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):169.66,161.33,142.98,129.88,125.95,125.18,77.23,43.94,36.44,34.27,31.94,31.93,31.57,30.06,29.68,29.66,29.61,29.37,29.34,26.41,22.72,14.16.
(2) Synthesis of Compound 5: in a dry two-necked flask, compound 3 (240 mg,0.54mmol,1.0 equiv.) 4- (2-octyldodecyl) thiophene pyrrole dione (4, 234mg,0.54mmol,1.0 equiv.) toluene (4 mL), glacial acetic acid (2 mL) and a stirrer were added under nitrogen. The reaction mixture was stirred at reflux temperature (120 ℃) for 12h until compound 4 was consumed. After the mixture was cooled to room temperature, it was poured into water, extracted three times with methylene chloride, dried over anhydrous magnesium sulfate, filtered and concentrated by a rotary evaporator. Petroleum ether was then used: dichloromethane (1:1) was used as eluent and purified by column chromatography on silica gel to give compound 5 (116 mg,0.13mmol,25% yield) as an off-black solid. 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):7.74(d,J＝4Hz,1H),7.62(d,J＝4Hz,1H),7.48(d,J＝4Hz,1H),6.77(d,J＝8Hz,1H),4.06(d,J＝8Hz,2H),3.68(d,J＝8Hz,2H),1.94(t,J＝8Hz,1H),1.87(t,J＝8Hz,1H),1.42-1.22(m,64H),0.89-0.84(m,10H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):207.02,169.91,166.50,160.21,153.16,138.78,138.12,132.43,130.77,130.05,129.92,126.53,118.52,117.35,111.28,46.16,44.65,37.07,36.40,35.93,31.95,31.93,31.89,31.63,31.45,30.97,30.04,29.97,29.80,29.71,29.68,29.65,29.63,29.60,29.55,29.39,29.36,29.31,29.27,27.23,26.41,26.38,25.56,22.71,22.68,14.16,14.15.
(3) Synthesis of monomer M1: in a clean two-necked flask, compound 5 (202 mg,0.23mmol,1.0 equiv.) was added, N, N-dimethylformamide (25 mL) and stirring until the solid was completely dissolved. N-bromosuccinimide (103 mg,0.58mmol,2.5 equiv.) is then added and reacted at room temperature under light-protected conditions for 24h until compound 5 is consumed. The mixture was concentrated using a rotary evaporator, then petroleum ether was used: dichloromethane (2:1) was used as eluent and purified by column chromatography on silica gel to give the dark blue solid, monomer M1 (134 mg,0.13mmol,56% yield). 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):7.71(s,1H),6.82(s,1H),4.02(d,J＝8Hz,2H),3.64(d,J＝8Hz,2H),1.91(d,J＝8Hz,1H),1.83(d,J＝8Hz,1H),1.40-1.23(m,64H),0.89-0.83(m,10H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):206.99,169.29,165.99,158.94,152.15,139.79,132.30,129.92,129.89,129.34,129.01,128.76,120.05,117.81,116.89,114.95,53.46,46.21,44.75,37.05,36.27,35.93,31.96,31.93,31.89,31.55,31.36,30.96,30.04,29.97,29.79,29.73,29.70,29.65,29.59,29.54,29.50,29.39,29.36,29.34,29.31,29.26,27.23,26.33,25.56,22.72,22.69,14.16,14.14.
(4) Synthesis of Polymer F1: into a dried round bottom flask were added monomer M1 (56 mg,0.055mmol,1.0 equiv.), monomer M2 (27.8 mg,0.056mmol,1.03 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (3.2 mg), which was operated three times by evacuating to replace nitrogen, and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the collected crude polymer was separated and purified by a soxhlet extractor using methanol, n-hexane and methylene dichloride as solvents in this order, and a concentrated solution of methylene dichloride phase was collected and precipitated in methanol, and a dark green solid, namely, polymer F1 (46 mg, 80%) was obtained by collecting the precipitate by filtration and drying.
The thermogravimetric and differential scanning calorimetry curve of the polymer F1 in this example 1 is shown in fig. 1, and the cyclic voltammogram and absorption spectrum of the polymer F1 in this example 1 is shown in fig. 2.
Example 2
Polymer F2 was prepared as follows:
(1) Compound 3 was prepared according to the procedure of example 1.
(2) Compound 5 was prepared according to the procedure of example 1.
(3) Monomer M1 was prepared as in example 1.
(4) Synthesis of polymer F2: into a dried round bottom flask were added monomer M1 (84 mg,0.082mmol,1.0 equiv.), monomer M3 (47.7 mg,0.082mmol,1.0 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (4.8 mg), which was then treated three times by evacuating to replace nitrogen, and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the collected crude polymer was separated and purified by a soxhlet extractor sequentially with methanol, n-hexane and dichloromethane as solvents, and a concentrated solution of the dichloromethane phase was collected to precipitate in methanol, and the precipitate was collected by filtration and dried to obtain a dark green solid, namely polymer F2 (39 mg, 53%).
The thermogravimetric and differential scanning calorimetry curve of the polymer F2 in this example 2 is shown in fig. 3, and the cyclic voltammogram and absorption spectrum of the polymer F2 in this example 2 is shown in fig. 4.
Example 3
Polymer F3 was prepared as follows:
(1) Synthesis of Compound 3: anhydride 11 (520 mg,3.1mmol,1.0 equiv.), 4-dimethylaminopyridine (DMAP, 156mg,1.3mmol,0.42 equiv.), o-xylene (10 mL) and mini-stirrer were added to a dry 10-20mL microwave reaction tube under nitrogen atmosphere, after which n-hexylamine (0.51 g,4.0mmol,1.3 equiv.) was added dropwise to the mixture for more than 15min, and the mixture was stirred for 15min until the solid was completely dissolved. The microwave reaction tube was then placed in a microwave reactor (P max =400W), the reaction was carried out by microwaves at 240 ℃ for 2h. The above procedure was repeated three more times and the four reaction mixtures were collected together, o-xylene was removed by rotary evaporator and petroleum ether was used: dichloromethane (1:1) was used as eluent and purified by column chromatography on silica gel to give compound 3 (1.0 g,5.0mmol,40% yieldd) as a dark red oily viscous liquid. 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):7.50(d,J＝4Hz,1H),7.28(d,J＝4Hz,1H),4.11(s,2H),3.92(t,J＝8Hz,2H),1.37-1.25(m,8H),0.90-0.86(m,3H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):207.05,169.34,160.94,143.02,129.85,125.85,125.22,40.02,34.25,31.51,30.98,29.34,27.98,26.70,22.57,19.77,14.08.
(2) Synthesis of Compound 5: in a dry two-necked flask, compound 3 (240 mg,0.54mmol,1.0 equiv.) was added, 4- (hexyl) thiophene pyrrole dione (4, 234mg,0.54mmol,1.0 equiv.), toluene (4 mL), glacial acetic acid (2 mL) and a stirrer under nitrogen. The reaction mixture was stirred at reflux temperature (120 ℃) for 12h until compound 3 was consumed. After the mixture was cooled to room temperature, it was poured into water, extracted three times with methylene chloride, dried over anhydrous magnesium sulfate, filtered and concentrated by a rotary evaporator. Thereafter using stone Oil ether: dichloromethane (1:1) was used as eluent and purified by column chromatography on silica gel to give compound 5 (116 mg,0.13mmol,25% yield) as an off-black solid. 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):7.75(d,J＝4Hz,1H),7.66(d,J＝4Hz,1H),7.50(d,J＝8Hz,1H),6.81(d,J＝4Hz,1H),4.12(s,J＝4Hz,2H),3.79(d,J＝4Hz,2H),1.43-1.25(m,16H),0.90-0.86(m,6H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):166.15,159.83,152.85,138.34,132.44,130.10,126.45,111.12,41.89,40.86,31.56,31.44,29.73,28.32,27.98,26.76,26.58,22.60,22.54,14.10,14.04.
(3) Synthesis of monomer M4: in a clean two-necked flask, compound 5 (157 mg,0.33mmol,1.0 equiv.) and N, N-dimethylformamide (25 mL) were added and stirred until the solid was completely dissolved. N-bromosuccinimide (148 mg,0.83mmol,2.5 equiv.) was then added and reacted at room temperature under light-protected conditions for 24h until compound 4 was consumed. The mixture was concentrated using a rotary evaporator, then petroleum ether was used: dichloromethane (2:1) was used as eluent and purified by column chromatography on silica gel to give the dark blue solid, monomer M4 (117 mg,0.19mmol,56% yield). 1 H NMR(chloroform-d,298K,400MHz,δ/ppm):7.69(s,1H),6.84(s,1H),4.06(t,J＝8Hz,2H),3.73(t,J＝8Hz,2H),1.40-1.25(m,16H),0.91-0.87(m,6H). 13 C NMR(chloroform-d,298K,100MHz,δ/ppm):168.94,165.58,158.52,151.80,139.72,132.26,129.29,128.98,128.89,120.09,117.71,116.76,114.75,41.99,40.99,31.54,31.40,28.31,27.88,26.74,26.54,22.62,22.53,14.10,14.03.
(4) Synthesis of Polymer F3: into a dry round bottom flask were added monomer M4 (18 mg,0.029mmol,1.0 equiv.), monomer M5 (36.4 mg,0.030mmol,1.03 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (1.7 mg), operated three times by evacuating nitrogen and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the crude polymer product obtained by collection was separated and purified by a Soxhlet extractor using methanol, n-hexane, methylene chloride and chloroform as solvents, and the concentrated solution of chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration and dried to obtain a dark blue solid, namely polymer F3 (36 mg, 90%).
The thermogravimetric and differential scanning calorimetry curve of the polymer F3 in this example 3 is shown in fig. 5, and the cyclic voltammogram and absorption spectrum of the polymer F3 in this example 3 is shown in fig. 6.
Example 4
Polymer F4 was prepared as follows:
(1) Compound 3 was prepared according to the procedure of example 3.
(2) Compound 5 was prepared according to the procedure of example 3.
(3) Monomer M4 was prepared as in example 3.
(4) Synthesis of Polymer F4: into a dry round bottom flask were added monomer M4 (18 mg,0.029mmol,1.0 equiv.), monomer M6 (31.1 mg,0.030mmol,1.03 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (1.7 mg), operated three times by evacuating nitrogen and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the crude polymer product obtained by collection was separated and purified by a Soxhlet extractor sequentially through methanol, n-hexane, dichloromethane and chloroform as solvents, and a concentrated solution of chloroform phase was collected and precipitated in methanol, and a dark blue solid, namely polymer F4 (32 mg, 92%) was obtained after the precipitate was collected by filtration and dried.
The thermogravimetric and differential scanning calorimetry curve of the polymer F4 in this example 4 is shown in fig. 7, and the cyclic voltammogram and absorption spectrum of the polymer F4 in this example 4 is shown in fig. 8.
Example 5
Polymer F5 was prepared as follows:
(1) Compound 3 was prepared according to the procedure of example 3.
(2) Compound 5 was prepared according to the procedure of example 3.
(3) Monomer M4 was prepared as in example 3.
(4) Synthesis of Polymer F5: into a dry round bottom flask were added monomer M4 (18 mg,0.029mmol,1.0 equiv.), monomer M7 (33.3 mg,0.030mmol,1.03 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (1.7 mg), operated three times by evacuating nitrogen and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the crude polymer product obtained by collection was separated and purified by a Soxhlet extractor sequentially through methanol, n-hexane, dichloromethane and chloroform as solvents, and the concentrated solution of chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration and dried to obtain a dark blue solid, namely polymer F5 (35 mg, 95%).
The thermogravimetric and differential scanning calorimetry curve of the polymer F5 in this example 5 is shown in fig. 9, and the cyclic voltammogram and absorption spectrum of the polymer F5 in this example 5 is shown in fig. 10.
Example 6
Polymer F6 was prepared as follows:
(1) Compound 3 was prepared according to the procedure of example 3.
(2) Compound 5 was prepared according to the procedure of example 3.
(3) Monomer M4 was prepared as in example 3.
(4) Synthesis of Polymer F6: into a dry round bottom flask were added monomer M4 (18 mg,0.029mmol,1.0 equiv.), monomer M8 (35.3 mg,0.030mmol,1.03 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (1.7 mg), operated three times by evacuating nitrogen and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the crude polymer product obtained by collection was separated and purified by a Soxhlet extractor sequentially through methanol, n-hexane, dichloromethane and chloroform as solvents, and the concentrated solution of chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration and dried to obtain a dark blue solid, namely polymer F5 (36 mg, 93%).
The thermogravimetric and differential scanning calorimetry curve of the polymer F6 in this example 6 is shown in fig. 11, and the cyclic voltammogram and absorption spectrum of the polymer F6 in this example 6 is shown in fig. 12.
Example 7
Polymer F7 was prepared as follows:
(1) Compound 3 was prepared according to the procedure of example 3.
(2) Compound 5 was prepared according to the procedure of example 3.
(3) Monomer M4 was prepared as in example 3.
(4) Synthesis of Polymer F7: into a dry round bottom flask were added monomer M4 (18 mg,0.029mmol,1.0 equiv.), monomer M9 (39.7 mg,0.030mmol,1.03 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (1.7 mg), operated three times by evacuating nitrogen and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the crude polymer product obtained by collection was separated and purified by a Soxhlet extractor sequentially through methanol, n-hexane, dichloromethane and chloroform as solvents, and a concentrated solution of chloroform phase was collected and precipitated in methanol, and a dark blue solid, namely polymer F7 (40 mg, 93%) was obtained after the precipitate was collected by filtration and dried.
The thermogravimetric and differential scanning calorimetry curve of the polymer F7 in this example 7 is shown in fig. 13, and the cyclic voltammogram and absorption spectrum of the polymer F7 in this example 7 is shown in fig. 14.
Example 8
Polymer F8 was prepared as follows:
(1) Compound 3 was prepared according to the procedure of example 3.
(2) Compound 5 was prepared according to the procedure of example 3.
(3) Monomer M4 was prepared as in example 3.
(4) Synthesis of Polymer F8: into a dry round bottom flask were added monomer M4 (18 mg,0.029mmol,1.0 equiv.), monomer M10 (35.0 mg,0.030mmol,1.03 equiv.) and catalyst tetrakis (triphenylphosphine) palladium (1.7 mg), operated three times by evacuating nitrogen and solvent ortho-xylene (5 mL); stirring the mixture solution at 140 ℃ for reaction for 12 hours, wherein the reaction is carried out under the nitrogen atmosphere; after the mixture solution is restored to room temperature, the obtained polymer solution is dripped into 150mL of methanol at the rate of 0.5mL/min, and polymer precipitation is obtained by filtering through filter paper, namely a polymer crude product; the crude polymer product obtained by collection was separated and purified by a Soxhlet extractor sequentially through methanol, n-hexane, dichloromethane and chloroform as solvents, and the concentrated solution of chloroform phase was collected and precipitated in methanol, and the precipitate was collected by filtration and dried to obtain a dark blue solid, namely polymer F8 (37 mg, 95%).
The thermogravimetric and differential scanning calorimetry curve of the polymer F8 in this example 8 is shown in fig. 15, and the cyclic voltammogram and absorption spectrum of the polymer F8 in this example 8 is shown in fig. 16.
Test example 1
The representative polymer F4 synthesized in example 4 was applied as an electron donor material in an organic solar cell device (ITO anode/anode interface layer/active layer/cathode interface layer/cathode).
Table 1 shows device performance parameters of organic solar cells prepared based on the polymer F4 as electron donor material and Y6 as electron acceptor material;
the device structure is as follows: ITO/PEDOT PSS/F4:Y6/PDINO/Ag.
Table 1 device performance parameters of the organic solar cell prepared based on example 4
Table 2 physical characterization data for the organic semiconducting polymers of examples 1-8
The polymers F1, F2, F3, F4, F5, F6, F7, F8 and F9 were subjected to a thermodynamic property test, a thermogravimetric curve test was carried out under the protection of nitrogen, and the polymer temperature was T with respect to a 5% mass loss temperature in the range of 30 to 600℃at a heating rate of 10℃per minute d The method comprises the steps of carrying out a first treatment on the surface of the The polymer was tested for differential calorimetric scan curves at a ramp rate of 10 ℃/min; the method comprises the steps of performing electrochemical performance test on a polymer, wherein a testing instrument is a CHI730e electrochemical workstation of Shanghai Chen Hua, a working electrode is a glassy carbon electrode, a counter electrode is a platinum wire, a reference electrode is silver/silver chloride, an electrolyte is an acetonitrile solution of 0.1M tetrabutyl hexafluorophosphonic acid amine, and ferrocene is used for calibration; the absorption spectrum of the polymer was measured by an ultraviolet-visible-near infrared spectrometer. Table 2 shows the physical characterizations based on the polymers F1, F2, F3, F4, F5, F6, F7, F8 and F9 According to, include HOMO, LUMO, eg, eg opt Td, and the position of the crystallization peak.
As can be seen from Table 2, the polymers F1, F2, F3, F4, F5, F6, F7, F8 and F9 have high thermal stability, the thermal decomposition temperatures are above 330 ℃, and no obvious endothermic or exothermic peak is generated in the range of 30-330 ℃; simultaneous optical bandgap Eg opt The optical band gaps are respectively 0.97eV, 0.57eV, 1.11eV, 1.08eV, 1.10eV, 1.08eV and 0.88eV, and are low; the HOMO is relatively high, namely-5.15 eV, -5.38eV, -5.23eV, -5.43eV, -5.16eV and-5.19 eV respectively; LUMO is lower, respectively, -3.70eV, -3.77eV, -3.88eV, -3.71eV, -3.76eV, -3.74eV, -3.75eV and-3.53 eV, so that eg=lumo-HOMO gives lower band gap Eg, respectively 1.45eV, 1.38eV, 1.27eV, 1.67eV, 1.47eV, 1.69eV, 1.41eV and 1.66eV. This indicates that the eight polymers have better thermal stability, optical properties and excellent electrochemical properties.
Using commercially available Y6 as acceptor for organic solar cells, polymer F4 as electron donor material, organic solar cell devices were prepared; ultrasonically cleaning a purchased ITO substrate by acetone and isopropanol in sequence, and then treating the ITO substrate in ultraviolet ozone for 10 minutes; placing the cleaned and blow-dried ITO substrate on a rotary table of a spin coater, spin-coating a PEDOT-PSSS aqueous solution on ITO conductive glass by adopting a solution spin coating method, and then drying for 15 minutes in the air at 150 ℃ to form a PEDOT-PSS film; f4 was taken in a glove box under nitrogen: y6 (w/w=1:1.2) was spin-deposited on PEDOT: forming an active layer film with the thickness of 60-120 nm on the PSS film; spin-coating PNDINO on the active layer film in a glove box in nitrogen atmosphere to form a film with the thickness of 20 nm; evaporating 100nm Ag under high vacuum condition to obtain anode electrode, and preparing solar cell with effective working area of 4mm 2 . All preparation processes were carried out in a glove box under nitrogen atmosphere. The device test is carried out under the irradiation of an Orie191192 type AM1.5 sunlight simulation lamp, and the radiance is 1kW/m 2 The J-V curve was tested using a Keithley model 2400 digital source list. Current-voltage curve of prepared positive battery deviceThe lines are shown in fig. 17, and the relevant data are listed in table 1. As can be seen from fig. 17 and table 1, the organic semiconductor polymer containing the thiophene pyridine isoindigo structure provided by the invention is used as a donor for an active layer, and can obtain higher open-circuit voltage and short-circuit current density, and obtain certain battery device performance.
Test example 2
The representative polymer F1 synthesized in example 1 was used as an active layer material in a Bottom Gate Bottom Contact (BGBC) organic field effect transistor device (Glass substrate/gate/dielectric/source drain/active layer).
Table 3 is the device performance parameters of an organic field effect transistor based on the polymer F1 as active layer material;
the device structure is as follows: glass/Al/CYTOP/Cr/Au/F1.
TABLE 3 device Performance parameters of organic field effect transistors prepared based on example 1
The glass substrate was sonicated with acetone and isopropyl alcohol for 10 minutes, then UV-treated for 30 minutes, the substrate was transferred into a glove box, and a layer of aluminum having a thickness of 50nm was evaporated on the substrate as a gate electrode. Followed by a top dielectric layer of about 400 nm. Source and drain electrodes (3nm Cr and 30nmAu) are fabricated on the dielectric layer using photolithographic techniques. A solution of the polymer in chlorobenzene (10 mg/mL) was then spin-coated onto the substrate while hot, and the polymer film was then annealed at 150℃for 10 minutes in a glove box. The field effect transistor performance of the devices was tested using a Keithley 4200SCS semiconductor tester in nitrogen. The output and transfer curves of the top gate-bottom contact devices prepared are shown in fig. 18, and the relevant data are listed in table 3. As can be seen from fig. 18 and table 3, the organic semiconductor polymer containing the thiophene pyridine isoindigo structure provided by the invention is used for the active layer of the organic field effect transistor, and can obtain higher carrier mobility and obtain certain performance of the field effect transistor.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. An organic semiconductor material containing a thiophene pyridine isoindigo structure, characterized in that the organic semiconductor material containing a thiophene pyridine isoindigo structure comprises:
wherein n is a natural number of 1 to 2000.
2. A method for preparing the thiophene pyridine isoindigo structure-containing organic semiconductor material according to claim 1, comprising the steps of:
s1, thienopyran-4, 6-dione and NH 2 R is mixed and subjected to addition reaction to obtain an intermediate a with a structure shown in a formula II;
s2, mixing the intermediate a with the structure shown in the formula II with thienopyrrole-4-alkyl-5, 6-dione, and performing condensation reaction to obtain an intermediate b with the structure shown in the formula III;
s3, carrying out bromination reaction on the intermediate b with the structure shown in the formula III and N-bromosuccinimide in an N, N-dimethylformamide solvent to obtain an intermediate c with the structure shown in the formula IV;
S4, mixing the intermediate c with the structure shown in the formula IV with H-pi-H, and performing Stille coupling reaction under the catalysis of a palladium catalyst to obtain the organic semiconductor material with the thiophene pyridine isoindigo structure shown in the claim 1;
wherein R, R' is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, triacontyl, isopropyl isobutyl, 2-ethylhexyl, 2-butylhexyl, 2-butyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-hexyldodecyl, 2-octyldecyl, 2-octyldodecyl, 2-octyltetradecyl, 2-octylhexadecyl, 2-decyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, or 2-dodecyloctadecyl, respectively.
3. The method for preparing an organic semiconductor material containing a thienopyridine isoindigo structure according to claim 2, wherein the molar ratio of thienopyran-4, 6-dione to NH2-R in step S1 is 1:1.0 to 1.1:0.30 to 0.35, and/or,
The addition reaction described in step S1 was carried out in an o-xylene solvent with a thienopyran-4, 6-dione to o-xylene dosage ratio of 3.8mmol:10 to 15mL, and/or,
the temperature of the addition reaction in the step S1 is 160-180 ℃, the reaction time is 10-14 h, and/or,
after the completion of the addition reaction described in step S1, the reaction solution is extracted with water and methylene chloride, then the lower organic phase is taken out, dried with anhydrous magnesium sulfate and filtered, the solvent is removed by a rotary evaporator to obtain a crude product, which is purified by column chromatography to obtain an intermediate a having a structure represented by formula ii, and/or,
the molar ratio of intermediate a to thienopyrrole-4-alkyl-5, 6-dione described in step S2 is 1:1.0 to 1.2, and/or,
the condensation reaction described in step S2 is carried out in the presence of a solvent which is a mixed solution of toluene, acetic acid, and/or,
the intermediate a and the thienopyrrole-4-alkyl-5, 6-dione described in step S2 are added to a mixed solution of toluene and acetic acid, reacted with stirring at 115 ℃, and/or,
the concentration of the mixed solution in the step S2 is 0.2-0.3 mol/L, and the volume ratio of toluene to acetic acid is 2:1, and/or,
The time of the condensation reaction in step S2 is 10 to 14 hours, and/or,
after the condensation reaction described in step S2 is completed, the reaction solution is poured into water to be quenched, extracted with water and methylene chloride, then the lower organic phase is taken out, dried with anhydrous magnesium sulfate and filtered, the solvent is removed by a rotary evaporator to obtain a crude product, the crude product is purified by column chromatography to obtain an intermediate b having a structure represented by formula iii, and/or,
the molar ratio of intermediate b to N-bromosuccinimide described in step S3 is 1:2.1 to 2.3, and/or,
the concentration of the intermediate b in the N, N-dimethylformamide solvent in the step S3 is 0.1 to 0.2mol/L, and/or,
the bromination reaction in step S3 is carried out at room temperature for 8 to 12 hours and/or,
the bromination reaction described in step S3 is carried out under light-shielding conditions, and/or,
after the bromination reaction described in step S3 is completed, the reaction solution is poured into water to be quenched, extracted with water and methylene chloride, then the lower organic phase is taken out, dried with anhydrous magnesium sulfate and filtered, the solvent is removed by a rotary evaporator to obtain a crude product, the crude product is purified by column chromatography to obtain an intermediate c having a structure shown in formula iv, and/or,
The molar ratio of intermediate c to H-pi-H described in step S4 is 1:1.0 to 1.1, and/or,
the palladium catalyst in step S4 is tetrakis (triphenylphosphine) palladium, and/or,
the molar ratio of the intermediate c to the palladium catalyst in the step S4 is 1:0.04 to 0.06, and/or,
the Stille coupling reaction described in step S4 is carried out in the presence of an organic solvent, which is o-xylene, and/or,
the ratio of the amount of intermediate c to ortho-xylene described in step S4 was 1mmol:50 to 150mL, and/or,
in the step S4, the intermediate c, H-pi-H and the palladium catalyst are mixed, the nitrogen is replaced by vacuumizing for three times, then o-xylene is added, and/or,
the Stille coupling reaction in the step S4 is carried out at the temperature of 120-160 ℃ for 36-72 h and/or,
the Stille coupling reaction described in step S4 is carried out in a nitrogen atmosphere, and/or,
after the Stille coupling reaction in the step S4 is completed, cooling the obtained reaction system to room temperature, dripping the reaction system into methanol to precipitate out a precipitate, and filtering to obtain a solid material, namely a crude product; purifying the crude product sequentially by methanol, normal hexane, dichloromethane and chloroform, dripping chloroform phase concentrate into methanol for secondary precipitation, filtering, and drying the obtained solid material to obtain the organic semiconductor material with the thiophene pyridine isoindigo structure shown in the formula I, wherein the organic semiconductor material is a deep blue solid, and/or,
The dropping speed in the step S4 is 0.4-0.6 mL/min.
4. The method for preparing an organic semiconductor material containing a thiophene pyridine isoindigo structure according to claim 3, wherein the o-xylene is anhydrous o-xylene, the intermediate a is reddish brown liquid, the toluene is anhydrous toluene, the intermediate b is black brown solid, the intermediate c is deep blue solid, and/or,
the addition reaction, condensation reaction and bromination reaction were carried out under stirring conditions and nitrogen atmosphere at a stirring speed of 450rpm.
5. The use of an organic semiconductor material containing a thiophene pyridine isoindigo structure according to claim 1 in the preparation of organic semiconductor thin films, organic photovoltaic cell devices, organic field effect transistor devices.
6. An organic semiconductor film, which is characterized by being formed by the solution of the organic semiconductor material containing the thiophene pyridine isoindigo structure according to the claim 1 or the organic semiconductor material containing the thiophene pyridine isoindigo structure prepared by the preparation method according to the claim 2.
7. An organic photovoltaic cell device comprising an electron donor material and an electron acceptor material, wherein the electron donor material or the electron acceptor material comprises the organic semiconductor material containing the thiophene pyridine isoindigo structure according to claim 1 or the organic semiconductor material containing the thiophene pyridine isoindigo structure prepared by the preparation method according to claim 2.
8. An organic field effect transistor device is characterized in that the active layer material comprises the organic semiconductor material containing the thiophene pyridine isoindigo structure according to claim 1 or the organic semiconductor material containing the thiophene pyridine isoindigo structure prepared by the preparation method according to claim 2.
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EP2644629B1 (en) * 2010-11-25 2018-11-07 Ocean's King Lighting Science&Technology Co., Ltd. Conjugated polymer containing isoindigo units, preparation method and use thereof

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CN103159926A (en) * 2011-12-09 2013-06-19 海洋王照明科技股份有限公司 Isoindigo based co-polymer organic semiconductor material, and preparation method and application thereof
CN103865041A (en) * 2012-12-12 2014-06-18 海洋王照明科技股份有限公司 Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof

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