CN115010731A - Schiff base nitrogen-doped functionalized PPAB molecule, application thereof and polymer for manufacturing organic photoelectric transistor - Google Patents

Schiff base nitrogen-doped functionalized PPAB molecule, application thereof and polymer for manufacturing organic photoelectric transistor Download PDF

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CN115010731A
CN115010731A CN202210434771.6A CN202210434771A CN115010731A CN 115010731 A CN115010731 A CN 115010731A CN 202210434771 A CN202210434771 A CN 202210434771A CN 115010731 A CN115010731 A CN 115010731A
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ppab
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郑萌
郎需霞
薄振海
时杰
张海昌
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Qingdao Bay Technology Industry Research Institute Co ltd
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Abstract

The invention discloses a Schiff base nitrogen-doped functionalized PPAB molecule, application thereof and polymerization for manufacturing an organic photoelectric transistor, wherein the PPAB molecule functionalized by Schiff base nitrogen is adopted in a polymer as an electron-withdrawing unit, the polymer is obtained by coupling DTS (DTS) used as an electron-donating unit and the PPAB molecule, so that the polymer has higher planarity, the introduction of DTS prolongs the conjugation length of the polymer, the polymer has higher carrier mobility and lower exciton binding energy, and the organic photoelectric transistor has higher photosensitivity when the polymer is adopted as an active and photosensitive layer of the organic photoelectric transistor.

Description

Schiff base nitrogen-doped functionalized PPAB molecule, application thereof and polymer for manufacturing organic photoelectric transistor
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a Schiff base nitrogen-doped functionalized PPAB molecule, application thereof and polymerization for manufacturing an organic photoelectric transistor.
Background
The phototransistor is used as an important optical sensor based on a field effect transistor, and has great application potential in the aspects of environmental monitoring, reverse sensors, photoelectric switches, photoelectric communication, night vision, full-color imaging and the like. The phototransistor incorporates both the photo-detectivity of the photodiode and the signal amplification function of the transistor, with higher photosensitivity and lower noise levels than photodiodes and photoconductors. Although inorganic (e.g., single crystal silicon, InAlAs-InGaAs) phototransistors have gained widespread attention in the industry and market, their development and use have been severely limited due to problems such as high temperature vacuum processes, poor compatibility with flexible liners, limited sensing fields, etc. Therefore, to realize low-cost, high-sensitivity, large-area, highly flexible phototransistors, attention has gradually turned to conjugated polymers.
Conjugated polymers are considered as an emerging solution processable and low cost semiconductor material with design flexibility, easily adjustable functional molecular design structure, and significant advantages such as large area and low cost device fabrication by spin coating. In recent years, the reported carrier mobility of the conjugated polymer is gradually higher than that of amorphous silicon (about 1 cm) through reasonably adjusting the electron energy level and the band gap, cutting the structure and optimizing the device 2 V -1 s -1 ). Through further research, the strong absorption band of the conjugated polymer determines the high-efficiency luminous energy of the current carrier under illumination, and the high carrier mobility ensures the high-efficiency transportation and collection of charges.
The present invention has been made in view of this situation.
Disclosure of Invention
One of the objectives of the present invention is to provide a schiff base aza functionalized PPAB molecule, which has higher planarity, therefore, has higher conjugation length, and is beneficial to improving carrier mobility.
Another object of the invention is to propose the use of Schiff base aza functionalized PPAB molecules as electron withdrawing units in organic phototransistors.
It is still another object of the present invention to provide a polymer for fabricating an organic phototransistor, the polymer being obtained by coupling reaction of PPAB molecules as electron withdrawing units DTS as electron donating units, and the organic phototransistor using the above polymer as active and photosensitive layers exhibits a significant photo-response to white light, and has better photosensitivity.
In order to achieve the above object, the first aspect of the present invention provides a schiff base aza-functionalized PPAB molecule, which has a structure represented by formula (1):
Figure BDA0003612413850000021
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of them being alkyl or alkoxy, R 5 Is a halogen atom.
Further, the PPAB molecule is obtained by carrying out an aminofluoroboration reaction on a substance 1, a substance 2 and boron trifluoride, wherein the structural formulas of the substance 1 and the substance 2 are respectively shown as a formula (2) and a formula (3):
Figure BDA0003612413850000031
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of them being alkyl or alkoxy, R 5 Is a halogen atom.
The structural formula of the preferred substance 2 is represented by the formula (3-1):
Figure BDA0003612413850000032
in the scheme, Br is used as a substituent, so that compared with other halogen elements, the cost is lower and the yield is higher.
Further, the substance 1 is prepared by the substitution reaction of 2-amino-3-hydroxypyridine and halogenated hydrocarbon, and the structural formula is shown as the formula (4):
Figure BDA0003612413850000041
wherein R is 1 Is of the molecular formula C n H 2n+1 The alkoxy of O, and the value range of n is 8-18.
The preparation process of the substance 1 comprises the following steps:
taking DMF as a solvent, mixing 2-amino-3-hydroxypyridine with halogenated hydrocarbon under the conditions of inert gas protection and sodium hydride activation, and carrying out substitution reaction to obtain a substance 1 with a structure shown as a formula (4), wherein the molar ratio of the 2-amino-3-hydroxypyridine to the halogenated hydrocarbon is (0.5-1.0): 1.
further, the preparation process of the substance 2 shown in the formula (3-1) is as follows:
under the condition of potassium tert-butoxide and tert-amyl alcohol, mixing 4-bromoxynil and diethyl succinate, and carrying out cyclization reaction to obtain the compound, wherein the molar ratio of the 4-bromoxynil to the diethyl succinate is (2.0-2.5): 1.
the second aspect of the present invention protects the use of the PPAB molecules of the above scheme in organic phototransistors, wherein the PPAB molecules act as electron withdrawing units of the polymer making up the active and photosensitive layers of the organic phototransistors.
The third aspect of the invention protects a polymer for manufacturing an organic phototransistor, wherein the polymer is obtained by coupling the PPAB molecule in the scheme as an electron-withdrawing unit with an electron-donating unit;
wherein the electron-donating unit is an electron-donating conjugated group, and the PPAB molecule passes through R 5 The group undergoes a coupling reaction with the electron donating unit.
Further, the electron supply unit is DTS, and the structural formula of the electron supply unit is shown as the formula (5):
Figure BDA0003612413850000051
wherein R is 6 Selected from the group consisting of those of the formula C i H 2i+1 Wherein i is in the range of 8-18.
R on PPAB molecule 5 Groups with-SnBu on DTS 3 The structure of the obtained polymer is shown in the formula (6) after the coupling reaction of the groups:
Figure BDA0003612413850000052
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of which is alkyl or alkoxy; r 6 Selected from the group consisting of those of the formula C i H 2i+1 Wherein i is in the range of 8-18.
Specifically, the preparation process of the polymer comprises the following steps: uniformly mixing the electron donating unit and the electron withdrawing unit according to a molar ratio of 1:1, and adding a catalyst to perform a coupling reaction to obtain a polymer shown as a formula (6); the kind of the catalyst is related to the group which generates the coupling reaction, in the invention, the catalyst is palladium catalyst; preferably, the palladium catalyst is palladium tetraphenylphosphonate.
Specifically, a solvent is mixed in an organic solvent according to a molar ratio of 1:1 for an electron donor unit and an electron withdrawing unit, then a palladium catalyst is added for coupling reaction, the ratio of the amount of the electron donor unit and the electron withdrawing unit to the volume of the organic solvent is 0.15mmol:0.15mmol:25ml, the reaction temperature of the coupling reaction is 90-100 ℃, and the reaction time is 48 hours.
Further, the above-mentioned polymers are used as active and photosensitiveThe organic phototransistor produced in layers exhibits a bipolar transfer characteristic having a value of 10 -3 cm 2 V -1 s -1 Hole mobility (μ) of h ) And 10 -4 cm 2 V -1 s -1 Electron mobility (μ) of e )。
The invention has the beneficial effects that:
the Schiff base nitrogen-doped functionalized PPAB molecule has better planarity, so that the effective conjugation length is longer, the carrier mobility of a polymer can be improved when the PPAB molecule is used as an electron-withdrawing unit, and meanwhile, the organic photoelectric transistor has good photosensitivity.
The PPAB molecule functionalized by Schiff base nitrogen serves as an electron-withdrawing unit, and the DTS serves as an electron-donating unit to prepare the polymer P-PPAB-DTS, which has lower HOMO energy level and LUMO energy level and can realize good hole injection for OFET devices; the polymer P-PPAB-DTS has a very low band gap, so that the polymer P-PPAB-DTS has more excellent conductivity and lower excitation energy.
Organic phototransistors employing the polymer P-PPAB-DTS as the active and photosensitive layer exhibit significant photoresponse to white light illumination, indicating excellent photosensitivity.
Drawings
FIG. 1 is a DSC curve of a polymer P-PPAB-DTS according to the present invention.
FIG. 2 is a TGA curve of the polymer P-PPAB-DTS of the present invention.
FIG. 3 shows an absorption spectrum of the polymer P-PPAB-DTS of the present invention in the state of a chloroform solution (S) and a polymer film (T).
FIG. 4 is a cyclic voltammogram of a Schiff base aza-functionalized PPAB molecule and a polymer P-PPAB-DTS deposited on an ITO electrolyte as a thin film.
FIG. 5 is an energy level diagram of a Schiff base nitrogen-functionalized PPAB molecule and a polymer P-PPAB-DTS.
Fig. 6 is a graph of the switching characteristics of an organic phototransistor employing the polymer P-PPAB-DTS as the active and photosensitive layers for a P-type scan region.
Fig. 7 is a graph of the switching characteristics of an organic phototransistor employing the polymer P-PPAB-DTS as the active and photosensitive layers for an n-type scan region.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings, and it will be understood by those skilled in the art that the following embodiments are only for explaining the technical principles of the present invention and are not intended to limit the scope of the present invention.
The invention provides a Schiff base nitrogen-doped functionalized PPAB molecule which can be used as an electron-withdrawing unit of a polymer for manufacturing an active and photosensitive layer of an organic phototransistor, and the structure of the PPAB molecule is shown as a formula (1):
a polymer for manufacturing an organic phototransistor, which has a structure represented by formula (1):
Figure BDA0003612413850000081
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of them being alkyl or alkoxy, R 5 Is a halogen atom.
The Schiff base nitrogen-doped functionalized PPAB molecule shown as the formula (1) has better main chain planarity and longer effective conjugation length in the molecule, is favorable for improving the carrier mobility of a polymer, and can be better applied to an organic photoelectric transistor. Further, the polymer shown in formula (1) still has higher photosensitivity with lower pi-pi stacking.
The present invention will be described in further detail with reference to specific examples.
As an embodiment of the present invention, this embodiment provides a schiff base aza-functionalized PPAB molecule, whose structure is shown in formula (1):
Figure BDA0003612413850000091
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of them being alkyl or alkoxy, R 5 Is a halogen atom.
Specifically, the PPAB molecule is obtained by carrying out an aminofluoroboration reaction on a substance 1, a substance 2 and boron trifluoride, wherein the structural formulas of the substance 1 and the substance 2 are respectively shown as a formula (2) and a formula (3):
Figure BDA0003612413850000092
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of them being alkyl or alkoxy, R 5 Is a halogen atom.
Specifically, in this embodiment, R in formula (1) or formula (2) 1 Is of the molecular formula C n H 2n+1 Alkoxy of O, R 2 、R 3 、R 4 Are hydrogen atoms, and the structures are respectively shown as a formula (1-1) and a formula (2-1):
Figure BDA0003612413850000101
r in the formula (3) in consideration of manufacturing cost and production difficulty 5 Is Br, and the structural formula is shown as (3-1):
Figure BDA0003612413850000111
the preparation method of the electron-withdrawing unit prepared by taking the formula (2-1) and the formula (3-1) as raw materials comprises the following steps:
s1, mixing 2-amino-3-hydroxypyridine with halogenated hydrocarbon under the condition of activating sodium hydride by using DMF as a solvent, and carrying out substitution reaction to obtain a substance 1 shown as a formula (2-1);
s2, under the condition of potassium tert-butoxide and tert-amyl alcohol, mixing 4-bromoxynil and diethyl succinate, and carrying out cyclization reaction to obtain a substance 2 shown in a formula (3-1);
s3, mixing the substances 1 and 2 with toluene as a solvent under the conditions of titanium tetrachloride and triethylamine, and adding boron trifluoride diethyl etherate to perform an aminofluoroboration reaction to obtain the PPAB molecule shown as the formula (1-1).
The more specific preparation process is as follows:
the preparation method of the substance 1 comprises the steps of mixing DMF and 7- (bromomethyl) pentadecane under the condition of protective gas, dissolving the 7- (bromomethyl) pentadecane in a DMF solvent by stirring to obtain a mixture A, then mixing 2-amino-3-hydroxypyridine and activated sodium hydride to obtain a mixture B, and slowly adding the mixture A into the mixture B for substitution reaction to obtain the substance 1, wherein the mode of slowly adding the substance A into the substance B is preferably dropwise adding, and the dropwise adding mode is not particularly limited and can be a dropwise adding mode well known by a person skilled in the art; the dropping rate is preferably 0.30-0.35 ml/min.
Preferably, the temperature for preparing mixture A is 25 ℃, the stirring duration is 2h, the protective gas is nitrogen, and the ratio of the molar amount of 7- (bromomethyl) pentadecane to the volume of DMF in mixture A is 35 mmol: 10 ml; the substitution reaction is carried out under the condition of keeping out of the sun, the reaction temperature is preferably 20-25 ℃, and the reaction time is preferably 28 hours; in the substitution reaction, the molar ratio of 2-amino-3-hydroxypyridine to activated sodium hydride is preferably 1: (2.15-2.45).
After the reaction has been completed, the product is subjected to a post-treatment, which preferably comprises: extracting the product to obtain an organic phase, drying the organic phase by using anhydrous magnesium sulfate, removing an organic solvent from the dried organic phase by using a rotary evaporation method to obtain a crude product, performing column chromatography purification on the obtained crude product, washing away residual DMF (dimethyl formamide) solvent and pigment by using n-hexane, washing the product by using methanol, and completely drying to obtain the substance 1; preferably, the extractant is water-chloroform.
Preferably, in the above process, the organic solvent in the organic phase is removed by a rotary evaporator to obtain a crude product; the column chromatography purification preferably uses silica gel, and the eluent for the column chromatography purification is preferably dichloromethane; the washing times of the n-hexane are preferably 3 times, and the washing times of the methane are preferably 3 times; the drying operation specifically comprises the following steps: drying is carried out by using a vacuum drying oven, the drying temperature is preferably set to be 40 ℃, and the drying time is preferably 12 hours.
Material 1 was obtained as a dark brown oil by the above method.
The preparation method of the substance 2 comprises the following steps: dissolving diethyl succinate in a tert-amyl alcohol solution under a protective gas condition to obtain a mixture C, and continuously stirring in the mixing process, wherein the mixing temperature is preferably 25 ℃, and the mixing time is preferably 2 hours; mixing potassium tert-butoxide and 4-bromoxynil to obtain a mixture D; then, the substance C is slowly added into the mixture D in a dropwise manner to carry out a cyclization reaction, so that a substance 2 is obtained.
In the above process, preferably, the protective gas is nitrogen; the ratio of the molar amount of diethyl succinate to the volume of tert-amyl alcohol in mixture C is preferably 50 mmol: 10 ml; the dropping rate is preferably 0.30-0.35 ml/min.
In the process of preparing the substance 2, the preferred molar ratio of the potassium tert-butoxide to the 4-bromoxynil is (1-1.02): 1; the temperature of the cyclization reaction is preferably 110-140 ℃, and the time is preferably 8 h.
After the reaction has been completed, the product is also subjected to a work-up treatment, which preferably comprises: performing solid-liquid separation, and sequentially washing the obtained solid substance with water and methanol to obtain a substance 2; the solid-liquid separation is not particularly limited, and the solid-liquid separation well known to the person skilled in the art can be adopted, specifically, such as suction filtration; the water washing and the methanol washing are not particularly limited in the invention, and the water washing and the methanol washing which are well known to those skilled in the art can be adopted; in the present invention, the number of times of the water washing is preferably 3 times; in the present invention, the number of methanol washes is preferably 3.
The substance 2 obtained by the above process was a red powdery solid.
The PPAB molecule is prepared by mixing the substance 1 and the substance 2 in a toluene solution under a protective gas condition to obtain a mixture E, adding titanium tetrachloride, triethylamine and boron trifluoride diethyl etherate into the mixture E, and carrying out an aminofluoroboration reaction to obtain the PPAB molecule.
Specifically, the substance 1 and the substance 2 are continuously stirred in the mixing process, the mixing temperature is preferably 110 ℃, and the mixing time is preferably 40 min; the protective gas is preferably nitrogen; the molar weight of substance 1 in mixture E and the volume ratio of the toluene solution are preferably 9 mmol: 180 ml; the molar amount of substance 2 and the volume ratio of the toluene solution are preferably 2 mmol: 180 ml; the toluene solution is preferably an anhydrous toluene solvent.
More specifically, the manner of adding titanium tetrachloride, triethylamine and boron trifluoride diethyl etherate into the mixture E is that the titanium tetrachloride is added into the mixture E, then the triethylamine is added into the mixture E, and then the boron trifluoride diethyl etherate is added into the mixture E; wherein the addition interval of the titanium tetrachloride and the triethylamine is preferably 5 min; the addition interval of triethylamine and boron trifluoride diethyl etherate is preferably 2 h; the molar ratio of titanium tetrachloride to triethylamine to boron trifluoride diethyl etherate is preferably 1: (2-3): (2-3).
In the preparation process of PPAB molecules, the reaction temperature of the aminofluoroboration reaction is preferably 123 ℃; the reflux reaction time of the aminofluoroboration reaction is preferably 18 hours; the progress of the reaction is preferably monitored by thin layer chromatography during the course of the reaction.
After the reaction has been completed, the product is subjected to a post-treatment, which preferably comprises: and extracting the product to obtain an organic phase, drying the obtained organic phase with anhydrous magnesium sulfate, removing the organic solvent from the dried organic phase with a rotary evaporation method to obtain a crude product, and purifying the obtained crude product by column chromatography to obtain the PPAB molecule.
In the present invention, the extractant for extraction is preferably water-dichloromethane. The extraction in the present invention is not particularly limited, and may be performed by extraction known to those skilled in the art.
The rotary evaporation method is a conventional method well known to those skilled in the art, i.e. a rotary evaporator is used to remove the organic solvent in the organic phase, and the crude product is obtained after completion.
In the present invention, silica gel is preferably used for column chromatography purification; the eluent for column chromatography purification is preferably dichloromethane and petroleum ether. The volume ratio of the eluting agent dichloromethane to the petroleum ether is preferably 1: (1-2).
The PPAB molecule prepared by the method is a blue solid.
The PPAB molecule prepared by the method can be used for manufacturing an organic photoelectric transistor, and particularly, the PPAB molecule is used as an electron-withdrawing unit of a polymer for manufacturing an active and photosensitive layer of the organic photoelectric transistor, and the polymer is obtained by coupling the PPAB molecule used as the electron-withdrawing unit with an electron-donating unit.
Furthermore, the electron donor unit is an electron donor conjugated group, and the invention is further described with DTS as the electron donor unit.
The electron supply unit is DTS, and the structural formula is shown as the formula (5):
Figure BDA0003612413850000151
wherein R is 6 Selected from those of the formula C i H 2i+1 The value range of i is 8-18, so that the solubility can be improved, and the prepared polymer has better performance.
Further, the structure of the polymer for manufacturing the organic phototransistor, which is prepared by using the PPAB molecule as the electron withdrawing unit and the DTS as the electron donating unit, is shown as formula (6):
Figure BDA0003612413850000152
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, andsub-formula is C n H 2n+1 Or of the formula C n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of which is alkyl or alkoxy; r 6 Selected from the group consisting of those of the formula C i H 2i+1 Wherein i is in the range of 8-18.
Specifically, the preparation process of the polymer shown in the formula (6) is as follows:
mixing PPAB molecules and DTS in a toluene solution under a protective atmosphere to obtain a mixture F, continuously stirring in the mixing process, wherein the mixing temperature is normal temperature, the stirring time is 5min, and the preferred molar weight ratio of the PPAB molecules to the DTS to the toluene is 0.15mmol:0.15mmol:25 ml; and then adding a palladium catalyst into the mixture F, and carrying out coupling reaction to obtain the polymer with the structural formula shown in the formula (6).
Preferably, in the above scheme, the protective gas is nitrogen; the toluene solution is preferably an anhydrous toluene solvent.
In the above coupling reaction, the molar weight ratio of the PPAB molecule, DTS and palladium tetraphenylphosphate is preferably 1:1: 0.02.
Specifically, in the coupling reaction process, the reaction temperature is preferably 90-100 ℃; the reaction time is preferably 48 h. Stirring is maintained continuously during the coupling reaction, which is preferably quenched with water at the end.
The stirring mentioned in the above-mentioned embodiment is not particularly limited, and may be stirring known to those skilled in the art.
After the coupling reaction, the product also needs to be post-treated, including: diluting the solution with a small amount of organic solvent, and filtering and washing with water; then, the mixture is dried by anhydrous magnesium sulfate, the dried product is dissolved in a small amount of dichloromethane again, methanol is used for precipitation, the precipitate is subjected to Soxhlet extraction and purification to remove oligomers and impurities, and finally, the polymer with the structural formula shown in the formula (6) is obtained by washing with chloroform.
In the above post-treatment process, the extraction is preferably performed by using a dichloromethane solution, preferably, the extraction comprises saturated concentrated salt water extraction and extraction washing, the number of times of saturated concentrated salt water extraction is preferably 2, and the number of times of water extraction is preferably 2
In the post-treatment process, a small amount of organic solvent diluted solution is preferably dichloromethane; the washing process is not particularly limited, and washing with water known to those skilled in the art is employed.
Drying the obtained organic phase by adopting anhydrous magnesium sulfate in the post-treatment process; the drying is preferably carried out under negative pressure conditions.
In the above work-up procedure, the precipitate is subjected to purification by Soxhlet extraction, preferably with the product being purified by Soxhlet extractors of methanol, n-hexane and THF. The Soxhlet extraction is not particularly limited in the present invention, and may be performed by a method known to those skilled in the art.
In the above-mentioned post-treatment, the number of washing with chloroform is preferably 3.
The polymer with the structure shown in the formula (6) obtained by the steps is a blue-black solid.
The above-described preparation process is described in further detail with specific examples.
Example one
This example provides a schiff base aza-functionalized PPAB molecule as an embodiment of the present invention, and the preparation process thereof is specifically as follows.
2-amino-3-hydroxypyridine (2.64g, 24mmol) and activated sodium hydride (1.40g, 58mmol) were weighed out under nitrogen and charged into a 500ml flask, after which distilled dry DMF solvent (180ml) was taken and poured into the flask. Stirring for 2 hours at room temperature, dissolving 7- (bromomethyl) pentadecane (10.69g, 35mmol) in 10ml of DMF solvent, mixing uniformly, slowly adding into a flask, reacting for 8 hours in a dark place, and obtaining a black brown solution after the reaction is finished; extracting with chloroform-water extraction system for 3 times, retaining organic layer, adding anhydrous magnesium sulfate, drying for 15min to remove residual water; and then further purifying the crude product by column chromatography, washing residual DMF solvent and pigment by using n-hexane, washing the product by using methanol, and completely drying to obtain a substance 1 shown as a structural formula (2-1), wherein the substance 1 is a dark brown oily product (3.82g, the yield is 47.6 percent), and the specific preparation reaction process is shown as a formula (7):
Figure BDA0003612413850000181
potassium tert-butoxide (11.5g,102.5mmol) and 4-bromoxynil (18.2g,100mmol) were added to a 250ml flask, and 180ml of a solution of tert-amyl alcohol was poured in, the temperature was raised to 110 ℃ and the mixture was thoroughly dissolved and stirred under nitrogen. After 2 hours, a solution of diethyl succinate (6.64ml,50mmol) in tert-amyl alcohol was slowly added dropwise for one hour; heating to 140 ℃, reacting for 5 hours until the solution is dark red, cooling to 60 ℃, and adding acetic acid; standing for half an hour, cooling, and performing suction filtration to obtain a dark red solid; washing the dark red solid with water and methanol for multiple times, and vacuum drying at 80 ℃ to obtain a substance 2 shown as a formula (3-1), wherein the substance 2 is a red powder solid (12.3g, the yield is 55.1%), and the specific preparation reaction process is shown as a formula (8):
Figure BDA0003612413850000182
material 1(3.0g, 9.0mmol) and material 2(0.89g, 2.0mmol) were weighed into a 250ml flask at room temperature under nitrogen, after which distilled dry toluene solution (180ml) was added. Subsequently, the mixture was heated to 110 ℃ and stirred for 40 minutes. Titanium tetrachloride (1.5ml, 13.5mmol) was then added to the mixture; after 5min, triethylamine (5.0ml, 35mmol) was added; when imine formation was confirmed by TLC analysis after 2 hours, boron trifluoride diethyl etherate (4.5ml, 36.5mmol) was added and the reaction temperature was raised to 123 ℃ and heated under reflux for 18 hours; after the reaction is finished, pouring the mixture into water, extracting the mixture by using dichloromethane, reserving a plurality of layers, drying the layers by using anhydrous magnesium sulfate, and removing residual water; then concentrated in vacuo to give a blue crude product; the crude product was purified on a silica gel column using dichloromethane to petroleum ether 1:1 as an eluent to obtain a PPAB molecule represented by formula (1-1) as a blue solid (0.655g, yield: 28%), which was specifically prepared according to the reaction procedure shown by formula (9):
Figure BDA0003612413850000191
further, the present invention also provides a polymer for fabricating an organic phototransistor, which is prepared by using the PPAB molecule described in the above scheme as an electron-withdrawing unit, as follows.
Example two
As another embodiment of the present invention, this embodiment provides a polymer for fabricating an organic phototransistor, using the PPAB molecule prepared in example two as an electron-withdrawing unit, wherein the structure of the polymer is shown in formula (6), and the preparation method thereof is specifically as follows.
Putting the Schiff base nitrogen-functionalized PPAB molecule (176mg, 0.15mmol) and DTS (136mg, 0.15mmol) into a 50ml flask, adding 20ml of toluene at room temperature under the protection of nitrogen, and stirring for about 10 min; subsequently, palladium tetraphenylphosphonate (3.5mg, 0.003mmol) was added to the reaction mixture. The mixture was stirred at 90 ℃ for 48 hours; the mixture was then cooled and extracted with a diluted solution of dichloromethane (50ml) (dark green), brine (2 × 50ml) and water (50 ml); the organic phase is then dried over magnesium sulfate and the solvent is evaporated; then, the polymer was again dissolved in DCM and precipitated with methanol to give a black solid, and the product was purified by soxhlet extraction of methanol, n-hexane and THF to remove oligomers and impurities; finally, washing was performed with chloroform to collect the product as a black solid (141mg, yield: 59%) to obtain a polymer having the structure represented by the formula (6).
The specific preparation reaction process is shown as the formula (10):
Figure BDA0003612413850000201
the polymer P-PPAB-DTS in formula 10 is only one of the products obtained by the above preparation method, and those skilled in the art can know that the products obtained by conventional replacement of the R groups in formulas (1) to (6) based on the above preparation method also fall within the scope of the present application.
The invention also provides an organic photoelectric transistor made of the polymer, which is concretely as follows.
EXAMPLE III
As another embodiment of the present invention, this example provides an organic phototransistor made using the polymer as described in example two, wherein the polymer P-PPAB-DTS acts as the active and photosensitive layer of the organic phototransistor.
Specifically, organic phototransistors are highly doped with silicon (Si) and SiO 2 As gate and gate dielectric, respectively, with source and drain electrodes formed by vacuum deposition on OTS-treated Si/SiO 2 A thin film of gold (about 30nm) was fabricated on the substrate, followed by deposition of a solution of P-PPAB-DTS polymer in toluene solution.
The above process was carried out in a nitrogen-filled glove box, and the polymer solution was thermally annealed on a hot stage at 180 ℃ for 10 minutes to remove solvent residues and obtain a high-quality polymer film.
Experimental example 1
In this experimental example, the performance of the polymer P-PPAB-DTS described in example two was tested, and the test results are shown in fig. 1 to 5. Specifically, as can be seen from fig. 1, the polymer P-PPAB-DTS has no distinct glass transition temperature Tg peak, which is due to the fact that the backbone of the polymer molecule has a large number of rigid groups such as benzene rings, resulting in the rigidity of the molecular structure itself; in addition, F atoms can form partial hydrogen bonds, so that strong intermolecular force is caused, the molecular movement capacity is limited, and an obvious Tg peak cannot be shown on a DSC curve; the 5% loss temperature of the polymer P-PPAB-DTS is shown in FIG. 2 as 316 ℃, which further illustrates the better thermal stability of the polymer P-PPAB-DTS.
Further, as can be seen from fig. 3, the polymer P-PPAB-DTS shows red shift in both chloroform solution and thin film state, wherein the red shift in thin film state indicates that the polymer P-PPAB-DTS has relatively good molecular planarity, and the polymer backbone thereof has better packing and aggregation state in solid state; the red shift in chloroform solution represents that the high planarity of the polymer P-PPAB-DTS leads to the increase of the effective conjugation length in the molecule, and according to the results, the polymer P-PPAB-DTS has better stacking and aggregation states and is beneficial to the effective charge transmission between adjacent polymers.
The HOMO and LUMO energy levels of the polymer P-PPAB-DTS and PPAB molecules are respectively calculated according to the redox curves of the polymer P-PPAB-DTS and PPAB molecules shown in FIG. 4 to obtain an energy level diagram shown in FIG. 5, and from FIG. 5, the HOMO and LUMO energy levels of the polymer P-PPAB-DTS are respectively-5.37 eV and-3.92 eV, and further, the band gap of the polymer P-PPAB-DTS is 1.45 eV.
Experimental example two
In this experimental example, the performance of the organic phototransistor manufactured in example three is tested, and the result of testing the performance of the constructed organic phototransistor is shown in fig. 6 and 7. As can be seen from FIGS. 6 and 7, the organic phototransistor using the P-PPAB-DTS polymer as the active and photosensitive layers showed a bipolar transfer characteristic having 10 -3 cm 2 V -1 s -1 Hole mobility (μ) of (2) h ) And 10 -4 cm 2 V -1 s -1 Electron mobility (μ) of e ) Meanwhile, the organic phototransistor based on the P-PPAB-DTS polymer as the active and photosensitive layer shows remarkable photoresponse to white light illumination, which shows that the organic phototransistor has better photosensitivity and can meet the requirement of the organic phototransistor on photosensitivity.
The above embodiments are only preferred embodiments of the present invention, and not intended to limit the present invention in any way, and although the present invention has been disclosed by the preferred embodiments, it is not intended to limit the present invention, and those skilled in the art can make various changes and modifications to the equivalent embodiments by using the technical contents disclosed above without departing from the technical scope of the present invention, and the embodiments in the above embodiments can be further combined or replaced, but any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still fall within the technical scope of the present invention.

Claims (10)

1. A Schiff base nitrogen-doped functionalized PPAB molecule is characterized by having a structure shown in a formula (1):
Figure FDA0003612413840000011
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Or of the formula C n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of them being alkyl or alkoxy, R 5 Is a halogen atom.
2. The Schiff base aza-functionalized PPAB molecule according to claim 1, wherein the PPAB molecule is obtained by aminofluoroboration of substance 1, substance 2 and boron trifluoride, wherein the structural formulas of substance 1 and substance 2 are represented by formula (2) and formula (3), respectively:
Figure FDA0003612413840000012
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of them being alkyl or alkoxy, R 5 Is a halogen atom.
3. The Schiff base aza-functionalized PPAB molecule according to claim 2, wherein the substance 1 is prepared by substitution reaction of 2-amino-3-hydroxypyridine and halogenated hydrocarbon, and the structural formula is shown as formula (4):
Figure FDA0003612413840000021
wherein R is 1 Is of the molecular formula C n H 2n+1 The alkoxy of O, the value range of n is 8-18.
4. The Schiff base nitrogen heterofunctionalized PPAB molecule according to claim 3, wherein the substance 1 is prepared by mixing 2-amino-3-hydroxypyridine and halogenated hydrocarbon under the condition of activating sodium hydride and taking DMF as a solvent under the protection of inert gas through substitution reaction;
wherein the molar ratio of the 2-amino-3-hydroxypyridine to the halogenated hydrocarbon is (0.5-1.0): 1.
5. use of a schiff-base aza-functionalized PPAB molecule as defined in any one of claims 1 to 4 for the preparation of an organic phototransistor.
6. A polymer for use in the production of an organic phototransistor, wherein the polymer is obtained by coupling a PPAB molecule according to any one of claims 1 to 4 as an electron-withdrawing unit with an electron-donating unit;
PPAB molecule by R 5 The group undergoes a coupling reaction with the electron donating unit.
7. The polymer for manufacturing an organic phototransistor as set forth in claim 6, wherein the electron donating unit is DTS having a structural formula shown in formula (5):
Figure FDA0003612413840000031
wherein R is 6 Selected from the group consisting of those of the formula C i H 2i+1 Wherein i is in the range of 8-18.
8. The method of claim 7 for making an organicA polymer of a phototransistor characterized by R at the PPAB molecule 5 Groups with-SnBu on DTS 3 The group is subjected to coupling reaction, and the structure of the product is shown as the formula (6):
Figure FDA0003612413840000032
wherein R is 1 、R 2 、R 3 、R 4 Selected from hydrogen, formula C n H 2n+1 Alkyl of formula C or n H 2n+1 Alkoxy of O, n ranges from 8 to 18, and R 1 、R 2 、R 3 、R 4 Only one of which is alkyl or alkoxy; r 6 Selected from the group consisting of those of the formula C i H 2i+1 Wherein i is in the range of 8-18.
9. The polymer molecule for use in the fabrication of an organic phototransistor according to claim 8, wherein the coupling reaction is performed under a protective atmosphere, in particular:
uniformly mixing the PPAB molecules and the DTS in an organic solvent according to the molar ratio of 1:1, then adding a palladium catalyst for coupling reaction, and carrying out post-treatment to obtain the polymer molecules;
preferably, the ratio of the amount of the PPAB molecule and DTS substance to the volume of the organic solvent is 0.15mmol:0.15mmol:25 ml.
10. The polymer molecule for manufacturing an organic phototransistor according to claim 9, wherein the reaction temperature of the coupling reaction is 90 to 100 ℃ and the reaction time is 48 hours.
CN202210434771.6A 2022-04-24 2022-04-24 Schiff base nitrogen-doped functionalized PPAB molecule, application thereof and polymer for manufacturing organic photoelectric transistor Pending CN115010731A (en)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FENG, RU ET AL.: "Near-infrared absorbing pyrrolopyrrole aza-BODIPY-based donor-acceptor polymers with reasonable photoresponse", JOURNAL OF MATERIALS CHEMISTRY C: MATERIALS FOR OPTICAL AND ELECTRONIC DEVICES, vol. 8, no. 26, 1 June 2020 (2020-06-01), pages 8770 - 8776, XP055744889, DOI: 10.1039/D0TC01487G *
YUTO KAGE ET AL.: "An Electron-Accepting aza-BODIPY-Based Donor-Acceptor-Donor Architecture for Bright NIR Emission", CHEMISTRY - A EUROPEAN JOURNAL, vol. 27, 19 February 2021 (2021-02-19), pages 5259 - 5267 *

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