CN115028812B - Polymer containing naphtho-bipyrazine-bisindene heterocyclic units, and preparation method and application thereof - Google Patents

Polymer containing naphtho-bipyrazine-bisindene heterocyclic units, and preparation method and application thereof Download PDF

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CN115028812B
CN115028812B CN202210724907.7A CN202210724907A CN115028812B CN 115028812 B CN115028812 B CN 115028812B CN 202210724907 A CN202210724907 A CN 202210724907A CN 115028812 B CN115028812 B CN 115028812B
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应磊
朱春光
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South China University of Technology SCUT
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Abstract

The invention discloses a polymer containing naphtho-bipyrazine-bisindene heterocyclic units, a preparation method and application thereof, wherein the preparation method comprises coupling reaction, selective reduction, condensation reaction, electrophilic substitution reaction and Stille coupling condensation reaction. The polymer containing the naphtho-bipyrazine-bisindene heterocyclic unit takes the naphtho-bipyrazine-bisindene heterocyclic unit as an acceptor unit, and the polymer material prepared by the polymer has good solubility, film forming property and thermal stability, can be applied to preparing an organic light detector device, shows the characteristic of lower dark current, and has wide commercial prospect in the fields of organic electronic devices, biomedical images and the like.

Description

Polymer containing naphtho-bipyrazine-bisindene heterocyclic units, and preparation method and application thereof
Technical Field
The invention relates to the field of polymer semiconductor materials, in particular to a polymer containing naphtho-bipyrazine-bisindene heterocyclic units, a preparation method and application thereof.
Background
The ultra-low band gap conjugated polymer has the advantages of extremely small optical band gap (< 1.0 eV), high electron affinity, low ion potential, ultra-wide spectrum corresponding characteristics (absorption spectrum is widened to near infrared or even infrared region) and the like, and has wide application prospects in the fields of bipolar field effect transistors, bipolar luminous field effect transistors, near infrared photodetectors, near infrared electrochromic devices, near infrared biological imaging and the like. Studies have shown that: the optical band gap of the polymer can be remarkably reduced by adopting an alternating copolymerization mode of the acceptor (A) unit with strong electricity deficiency characteristic and the donor (D) unit with strong electricity deficiency characteristic, and the D-A type ultra-low band gap conjugated polymer can be further constructed. Currently, the acceptor building blocks for ultra-low band gap conjugated polymers are mainly focused on thiazole and pyrazine ring acceptor units, such as benzobisthiadiazole (BBT, J.Am.Chem.Soc.,2011,133,20799), thienopyrazine (TP, chem.Commun.,2011,47,11394), thienothiazole (TTZ, appl.Phys.Lett.,2006,89,081106), compared to the donor (D) units of strongly rich electrical properties. Therefore, the receptor building blocks available for construction of ultra-low band gap conjugated polymers are scarce, which has also attracted considerable attention from many researchers. In the face of the research problem of scarcity of the electron-deficient units, the further development of novel electron-deficient receptor units and the ultra-low band gap conjugated polymers thereof has very important significance.
Disclosure of Invention
Aiming at the challenges of few types of ultralow band gap conjugated polymer materials, scarcity of receptor building units, high dark current density and the like, the invention provides a polymer containing a naphtho-bipyrazine-bisindene heterocyclic unit, a preparation method and application thereof.
In order to solve the technical problems, the invention provides a polymer containing a naphtho-bipyrazino-bisindene heterocyclic unit, which has a structural formula as shown in the following formula I or formula II:
Figure BDA0003712931220000011
/>
Figure BDA0003712931220000021
in the formula I and the formula II, R is a straight-chain alkyl group with the total number of carbon atoms being 6-16 or a branched-chain alkyl group with the total number of carbon atoms being 8-30;
ar is one of the structures shown below, but is not limited to the following structural formula, wherein R in Ar is defined as in formula I and formula II;
Figure BDA0003712931220000022
in the formula I and the formula II, n is an integer of 10-300.
The above-mentioned polymer containing naphthyridin bisindene heterocyclic units, preferably, the straight-chain alkyl group having a total number of carbon atoms of 6 to 16 is specifically: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl;
the branched alkyl group having a total number of carbon atoms of 8 to 30 is specifically: 2-ethylhexyl, 2-hexyl-octyl, 4-hexyl-decyl, 3-hexyl-undecyl, 2-octyl-decyl, 2-octyl-dodecyl, 3-octyl-tridecyl, 2-decyl-dodecyl, 2-decyl-tetradecyl, 3-decyl-pentadecyl, 2-dodecyl-hexadecyl, 4-octyl-tetradecyl, 4-decyl-hexadecyl, 4-hexyl-decyl, 4-octyl-dodecyl, 4-decyl-tetradecyl or 4-dodecyl-hexadecyl; n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl.
The above-mentioned polymer containing a naphthyridobipyrazinodiindene heterocyclic unit, preferably, the polymer containing a naphthyridobipyrazinodiindene heterocyclic unit is PNAT1, and the PNAT1 has the structural formula of the following formula III:
Figure BDA0003712931220000031
in the formula III, n is an integer of 10 to 300.
The above-mentioned polymer containing a naphthyridobipyrazinodiindene heterocyclic unit, preferably, the polymer containing a naphthyridobipyrazinodiindene heterocyclic unit is PNAT2, and the PNAT2 has a structural formula of the following formula IV:
Figure BDA0003712931220000032
in the formula IV, n is an integer of 10 to 300.
As a general technical idea, the present invention also provides a method for preparing the above polymer containing a naphthyridin bisindene heterocyclic unit, comprising the steps of:
s1, mixing 2-tributyltin-4-alkylthiophene with 5, 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole and carrying out palladium catalysis Stille coupling reaction to obtain an intermediate a;
s2, selectively reducing the intermediate a by using reduced zinc powder to obtain an intermediate b;
s3, carrying out condensation reaction on the intermediate b and ninhydrin hydrate to obtain an intermediate c or an intermediate d;
s4, carrying out nucleophilic substitution reaction on the intermediate c or the intermediate d under the action of malononitrile to obtain a compound e and a compound f respectively;
s5, performing electrophilic substitution reaction on the compound e or the compound f and N-bromosuccinimide to obtain a compound M respectively 1 And compound M 2 ，
S6, subjecting the compound M 1 Or a compound M 2 Carrying out Stille coupling condensation reaction with a dimethyltin group substituted aromatic heterocyclic monomer g under the action of a palladium catalyst to respectively obtain polymers containing benzobipyrazinodiindene heterocyclic units with structural formulas shown in formulas I and II;
wherein the structural formula of the intermediate a is as follows:
Figure BDA0003712931220000041
the structural formula of the intermediate b is as follows:
Figure BDA0003712931220000042
the structural formula of the intermediate c is as follows:
Figure BDA0003712931220000043
the structural formula of the intermediate d is as follows:
Figure BDA0003712931220000044
the structural formula of the compound e is as follows:
Figure BDA0003712931220000051
the structural formula of the compound f is as follows:
Figure BDA0003712931220000052
the compound M 1 The structural formula is as follows:
Figure BDA0003712931220000053
the compound M 2 The structural formula is as follows:
Figure BDA0003712931220000061
the structural formula of the dimethyltin group substituted aromatic heterocyclic monomer g is as follows:
Figure BDA0003712931220000062
wherein R is a straight-chain alkyl group with the total number of carbon atoms of 6-16 or a branched-chain alkyl group with the total number of carbon atoms of 8-30;
ar is one of the structures shown below, but is not limited to the following structural formula, wherein R in Ar is defined as in formula I and formula II;
Figure BDA0003712931220000063
and n is an integer of 10-300.
In the above preparation method, preferably, the S1 specifically is: mixing 2-tributyltin-4-alkylthiophene, 5, 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole, palladium catalyst and solvent under the protection of nitrogen, and refluxing and stirring for 3-10 hours to obtain an intermediate a; the mass ratio of the 5, 10-dibromonaphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole, 2-tributyltin-4-alkyl thiophene and the palladium catalyst is 1.0:2.0-3.0:0.01-0.1;
in the above preparation method, preferably, the S2 specifically is: under the protection of nitrogen, mixing the intermediate a, the reduced zinc powder and the solvent, and refluxing and stirring for 3-10 hours to obtain an intermediate b;
in the above preparation method, preferably, the S3 specifically is: adding the intermediate b and ninhydrin into a solvent, mixing, refluxing and stirring for 1-3 hours, and cooling to obtain an intermediate c and an intermediate d; the mass ratio of the compound b to the ninhydrin is 1.0:3.0-10.0;
in the above preparation method, preferably, the S4 specifically is: mixing an intermediate c or an intermediate d, malononitrile, methylene dichloride and pyridine under the protection of nitrogen, slowly adding titanium tetrachloride, and stirring at 40 ℃ for reaction for 10-20 hours to obtain a compound e and a compound f respectively; the mass ratio of the intermediate c or the intermediate d to pyridine and malononitrile is 1.0:4.0-10.0:0.5-1.0;
in the above preparation method, preferably, the S5 specifically is: mixing the compound e or the compound f with a solvent under the protection of nitrogen; then adding N-bromosuccinimide into the mixed solution, stirring and reacting for 5-10 hours at room temperature to respectively obtain a compound M 1 And compound M 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the compound e or the compound f to the N-bromosuccinimide is 1:2.0-3.0;
in the above preparation method, preferably, the S6 specifically is: subjecting the compound M 1 Or a compound M 2 Mixing a dimethyltin group substituted aromatic heterocyclic monomer g, a solvent and a palladium catalyst, and stirring and reacting for 24-72 hours at 80-150 ℃ under the protection of nitrogen to obtain a polymer containing a naphthyridin bisindene heterocyclic unit; the mass ratio of the compound M1 or M2, the dimethyltin group substituted aromatic heterocyclic monomer g and the palladium catalyst is 1:1.0-1.5:0.01-0.1.
In the above preparation method, preferably, the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium.
In the above preparation method, preferably, the solvent is one or more of toluene, xylene, N '-dimethylformamide, N' -dimethylacetamide, chlorobenzene, dichlorobenzene, trichlorobenzene and tetrahydrofuran.
As a general technical concept, the invention also provides application of the polymer containing the naphthacene bipyrazine bisindene heterocyclic unit in preparation of an organic photoelectric detector device.
The application is specifically that a polymer material containing a naphtho-bipyrazino-bisindene heterocyclic unit and an electron donor material are prepared into an active layer, wherein the molar ratio of the polymer material containing the naphtho-bipyrazino-bisindene heterocyclic unit to the electron donor material is 1-1.5:1, and then the active layer is used in an organic photodetector device.
The electron donor material is an organic electron donor material; the electron donor material is at least one of PCE10, PCE12 and P3 HT.
Figure BDA0003712931220000071
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method of the polymer containing the naphthacene bipyrazine bisindene heterocyclic unit has the advantages of strong universality, mild synthesis conditions, high synthesis yield and the like, and can be popularized and applied to the industrial amplification synthesis and production;
(2) The polymer material containing the naphtho-bipyrazine-bisindene heterocyclic unit provided by the invention has a large pi conjugated skeleton of a heteroatom, can enhance pi-pi interaction in molecules and among molecules, and improves carrier mobility;
(3) According to the polymer material containing the naphtho-bipyrazine-bisindene heterocyclic unit, which is provided by the invention, due to the fact that electron-deficient acceptor units are introduced, the material has a lower HOMO energy level;
(4) The polymer material containing the naphthacene bipyrazinodiindene heterocyclic unit has wide commercial prospect in the organic electronics field such as organic light detectors and the like;
(7) The polymer material containing naphthacene bipyrazine bisindene heterocyclic unit provided by the invention is used as an active layer of a device, and the dark current density of an organic photodetector is 10 -7 mA/cm 2 The following fully reveals a class of polymer materials containing naphthyridin bisindene heterocyclic unitsThe advantage of the material.
Drawings
FIG. 1 is an absorption spectrum of a solid film of a polymer material PAN1 containing a naphthacenedi pyrazinodiindene heterocyclic unit prepared in example 1 in chloroform solution and a quartz plate;
FIG. 2 is an absorption spectrum of a polymer material PANT2 containing naphthacene bisindene heterocyclic units prepared in example 2 in chloroform solution and a solid film on a quartz plate;
FIG. 3 is a schematic structural diagram of an organic photodetector device with the polymer materials PANT1 and PANT2 containing naphthacene bisindene heterocyclic units prepared in examples 1 and 2 as organic active layers;
FIG. 4 is a J-V curve of an organic photodetector having a class of polymer materials PANT1 and PANT2 containing naphthacenebisindene heterocyclic units prepared in examples 1 and 2 as an organic active semiconductor layer;
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby. The examples described below are intended to facilitate an understanding of the invention and are not intended to be in any way limiting. The methods are conventional methods unless otherwise specified. The reaction materials can be purchased from published commercial sources unless otherwise specified.
Example 1:
the invention discloses a polymer PNAT1 containing naphthacene bispyrazinodiindene heterocyclic units, wherein the PNAT1 has a structural general formula shown in a formula I:
Figure BDA0003712931220000091
wherein R is decyl and Ar is
Figure BDA0003712931220000092
/>
The specific structural formula of PNAT1 is:
Figure BDA0003712931220000093
the synthetic route of PNAT1 is:
Figure BDA0003712931220000101
the method specifically comprises the following steps:
(1) Synthesis of intermediate a: to a three-necked flask was added 2-tributylstannyl-4-decylthiophene (6.22 mmol), 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole (2.49 mmol), bis (triphenylphosphine) palladium dichloride (0.25 mmol), and 50mL toluene solvent under nitrogen. After the reaction was stirred at reflux for 3 hours, it was cooled to room temperature. The organic phase was extracted with dichloromethane and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was dried to give a crude product. Purifying with silica gel column (eluting solvent is petroleum ether: dichloromethane=5:1, v:v) to obtain red solid as intermediate a (yield=82%).
Intermediate a structure characterization data are as follows:
MALDI-TOF-MS:m/z[M] + calcd for(C 38 H 48 N 4 S 4 ):689.07；found:689.12.
from the above, the structure of the compound was correct, and the compound was the intermediate a shown.
(2) Synthesis of intermediate c: to a three-necked flask was added intermediate a (1.45 mmol), reduced zinc powder (43.54 mmol) and 30mL of acetic acid solvent under nitrogen. After the reaction was stirred at reflux for 5 hours, it was cooled to room temperature. The excess zinc powder is filtered off, the organic phase is extracted with ethyl acetate, dried over anhydrous magnesium sulfate and the solvent is spun dry to obtain the amine compound intermediate b.
Then, the resulting amine intermediate b and ninhydrin (5.75 mmol) were added to a three-necked flask containing 20mL of ethanol solution for reaction, and after stirring under reflux for 12 hours, the reaction was cooled to room temperature. Extracting with dichloromethane, drying with anhydrous magnesium sulfate, drying under reduced pressure, and purifying with silica gel chromatographic column (petroleum ether as eluent: dichloromethane=2:1, V: V) to obtain green solid as intermediate c (yield=45%).
Intermediate c structure characterization data are as follows:
HRMS(MALDI-TOF):m/z[M] + calcd for(C 71 H 106 N 4 OS 3 ):881.21；found:881.10。
from the above, the structure of the compound was correct, which was the intermediate c shown.
(3) Synthesis of intermediate e: to a three-necked flask, intermediate c (1.13 mmol), malononitrile (5.67 mmol), 50mL of methylene chloride and 3mL of pyridine were sequentially added under nitrogen, and finally 0.5mL of titanium tetrachloride was slowly added. After stirring the reaction at 40℃for 15 hours, it was cooled to room temperature. Extracting with dichloromethane and saturated saline, drying the organic phase with anhydrous magnesium sulfate, and spin-drying under reduced pressure, purifying the crude product with silica gel column chromatography (eluent is petroleum ether: dichloromethane=2:1, v:v) to obtain dark brown solid as intermediate e (yield=82%).
Intermediate e structure characterization data are as follows:
HRMS(MALDI-TOF):m/z[M] + calcd for(C 71 H 106 N 4 OS 3 ):977.31；found:977.24。
from the above, the structure of the compound was correct, which was the intermediate e shown.
(4) Compound M 1 Is synthesized by the following steps: to a three-necked flask containing chloroform and N, N' -dimethylformamide under nitrogen atmosphere was added intermediate e (1.02 mmol), which was stirred in an ice bath. Then, N-bromosuccinimide (2.25 mmol) was dissolved in 5mL of N, N' -dimethylformamide to obtain a mixed solution, and the mixed solution was slowly dropped into the reaction solution by a syringe. After stirring at room temperature for 12 hours, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was dried under reduced pressure. Purifying the crude product with silica gel column (petroleum ether: dichloromethane=2:1, V: V) to obtain brown solid, which is monomer compound M 1 (yield = 71%).
Compound M 1 The structural characterization data is as follows,
HRMS(MALDI-TOF):m/z[M] + calcd for(C 71 H 104 Br 2 N 4 OS 3 ):1135.10；found:1135.01。
from the above, the compound has the correct structure, and is the compound M 1 。
(5) Synthesis of Polymer PNA 1: by combining the monomer compounds M 1 (0.176 mmol), 2, 5-bis (trimethyltin) thiophene (0.352 mmol), 6mg of tris (dibenzylideneacetone) dipalladium, 9mg of tris (o-methylphenyl) phosphorus and 3mL of chlorobenzene were subjected to three freeze-pump-thaw cycles under argon to remove oxygen. The reaction was stirred at 115℃for 72h under nitrogen and cooled to room temperature. 200mL of methanol was added thereto, stirred at room temperature for 0.5h, suction-filtered, and the obtained polymer was extracted in a Soxhlet extractor. Sequentially extracting with methanol, acetone and petroleum ether to colorless, removing small molecules and catalyst, extracting with chloroform, and spin-drying chloroform to obtain black solid with metallic luster, namely PNAT1 (yield=90%).
The molecular weight and molecular weight distribution are as follows: weight average molecular weight M w 29.9kDa, number average molecular weight M n Is 13.1kDa, and the polymer has a molecular weight distribution index of 2.25.
Example 2:
the invention relates to a polymer PNAT2 containing naphthacene bispyrazinodiindene heterocyclic units, wherein the PNAT2 has a structural general formula II:
Figure BDA0003712931220000121
wherein R is decyl and Ar is
Figure BDA0003712931220000122
The specific structural formula of PNAT2 is:
Figure BDA0003712931220000123
the synthetic route of PNAT2 is:
Figure BDA0003712931220000131
the method specifically comprises the following steps:
(1) Synthesis of intermediate a: synthesized by the synthesis method described in example 1.
(2) Synthesis of intermediate d: to a three-necked flask was added intermediate a (1.45 mmol), reduced zinc powder (43.54 mmol) and 30mL of acetic acid solvent under nitrogen. After the reaction was stirred at reflux for 5 hours, it was cooled to room temperature. The excess zinc powder is filtered off, the organic phase is extracted with ethyl acetate, dried over anhydrous magnesium sulfate and the solvent is spun dry to obtain the amine compound intermediate b. Then, the resulting amine intermediate b and ninhydrin (5.75 mmol) were added to a three-necked flask containing 20mL of ethanol solution for reaction, and after stirring under reflux for 12 hours, the reaction was cooled to room temperature. Extracting with dichloromethane, drying with anhydrous magnesium sulfate, drying under reduced pressure, and purifying with silica gel chromatographic column (petroleum ether as eluent: dichloromethane=2:1, V:V) to obtain dark green solid as intermediate d (yield=35%).
Intermediate d structure characterization data are as follows:
HRMS(MALDI-TOF):m/z[M] + calcd for(C 71 H 106 N 4 OS 3 ):881.21；found:881.35。
from the above, the structure of the compound was correct, which was the intermediate d shown.
(3) Synthesis of intermediate f: to a three-necked flask, intermediate c (1.13 mmol), malononitrile (5.67 mmol), 50mL of methylene chloride and 3mL of pyridine were sequentially added under nitrogen, and finally 0.5mL of titanium tetrachloride was slowly added. After stirring the reaction at 40℃for 15 hours, it was cooled to room temperature. Extracting with dichloromethane and saturated saline, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent under reduced pressure, purifying the crude product with silica gel column (eluent is petroleum ether: dichloromethane=2:1, V: V) to obtain brown solid, namely intermediate e (yield=75%).
Intermediate e structure characterization data are as follows:
HRMS(MALDI-TOF):m/z[M] + calcd for(C 71 H 106 N 4 OS 3 ):977.31；found:977.46。
from the above, the structure of the compound was correct, and the compound was the intermediate f shown.
(4) Compound M 2 Is synthesized by the following steps: to a three-necked flask containing chloroform and N, N' -dimethylformamide under nitrogen atmosphere was added intermediate e (1.02 mmol), which was stirred in an ice bath. Then, N-bromosuccinimide (2.25 mmol) was dissolved in 5mL of N, N' -dimethylformamide to obtain a mixed solution, and the mixed solution was slowly dropped into the reaction solution by a syringe. After stirring at room temperature for 12 hours, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was dried under reduced pressure. Purifying the crude product with silica gel column (petroleum ether: dichloromethane=2:1, V: V) to obtain brown solid, which is monomer compound M 2 (yield = 81%).
Compound M 2 The structural characterization data is as follows,
HRMS(MALDI-TOF):m/z[M] + calcd for(C 71 H 104 Br 2 N 4 OS 3 ):1135.10；found:1135.67。
from the above, the compound has the correct structure, and is the compound M 2 。
(5) Synthesis of Polymer PNA 2: by combining the monomer compounds M 2 (0.176 mmol), 2, 5-bis (trimethyltin) thiophene (0.352 mmol), 6mg of tris (dibenzylideneacetone) dipalladium, 9mg of tris (o-methylphenyl) phosphorus and 3mL of chlorobenzene were subjected to three freeze-pump-thaw cycles under argon to remove oxygen. The reaction was stirred at 115℃for 72h under nitrogen and cooled to room temperature. 200mL of methanol was added thereto, stirred at room temperature for 0.5h, suction-filtered, and the obtained polymer was extracted in a Soxhlet extractor. Sequentially extracting with methanol, acetone and petroleum ether to colorless, removing small molecules and catalyst, extracting with chloroform, and spin-drying chloroform to obtain black solid with metallic luster, namely PNAT2 (yield=80%).
The molecular weight and molecular weight distribution are as follows: weight average molecular weight M w 39.9kDa, number average molecular weight M n 20.1kDa, the polymer has a molecular weight distribution index of 1.98.
Determination of spectral Properties and organic photodetector Properties of polymers PANT1 and PANT2 containing naphthalocyanine biindene heterocyclic units prepared in examples 1 and 2 above:
(1) Absorption spectrum property of polymer PANT1 containing naphthacene bipyrazine bisindene heterocyclic unit
Fig. 1 is an ultraviolet-visible-near infrared absorption spectrum of a film of a polymer PANT1 containing a naphtho-bipyrazino-bisindene heterocyclic unit on a chloroform solution and a quartz plate (the film is prepared by spin-coating a chloroform solution on the quartz plate). As can be seen from FIG. 1, the polymer PANT1 solution containing naphthyridine bisindene heterocyclic unit and the film both show a wide absorption range, the maximum absorption sideband value of the film absorption is about 1266nm, the corresponding optical band gap is 0.98eV (the optical band gap is according to formula E g Calculation of 1240/lambda, wherein E g For optical band gap, λ is the film absorption maximum absorption sideband value).
(2) Absorption spectrum property of polymer PANT2 containing naphthacene bipyrazine bisindene heterocyclic unit
Fig. 2 is an ultraviolet-visible-near infrared absorption spectrum of a class of polymer PANT2 containing naphthacenedi pyrazinodiindene heterocyclic units in chloroform solution and a film on a quartz plate (the film is prepared by spin coating a chloroform solution on the quartz plate). As can be seen from FIG. 2, the polymer PANT2 solution containing naphthyridine bi-indene heterocyclic units and the film both show a wide absorption range, the maximum absorption sideband value of the film absorption is about 1294nm, the corresponding optical band gap is 0.96eV (the optical band gap is according to the formula E g Calculation of 1240/lambda, wherein E g For optical band gap, λ is the film absorption maximum absorption sideband value).
(3) Organic photodetector Performance determination of polymers PANT1 and PANT2
The invention adopts the device structure shown in figure 3 to study the semiconductor characteristics of the polymer film in the organic photodetector. The preparation method of the device comprises the following steps: taking Indium Tin Oxide (ITO) glass with the square resistance of 10 omega, sequentially carrying out ultrasonic cleaning by using acetone, a detergent, deionized water and isopropanol, and carrying out plasma treatment for 10 minutes; spin-coating a polyethoxy thiophene (PEDOT: pss=1:6, w/w) film doped with polystyrene sulfonic acid on ITO, and drying the film at 80 ℃ in a vacuum oven for 8 hours, wherein the thickness of the film is 30 nm; the polymer was then brought to PC71 BM=1:1.5The w/w chlorobenzene solution (2 wt.%) is spin-coated on the surface of PEDOT: PSS film, the thickness is 100nm, as active layer; finally, sequentially evaporating a layer of Ca with the thickness of 10nm and a layer of metal Al with the thickness of 100nm on the active layer, and forming a device structure: ITO/PEDOT PSS/Polymer PC71BM/Ca/Al. The test results are shown in fig. 4: dark current J at-0.1V for devices with Polymer PANT1 as active layer sc 1.4X10 -8 mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Dark current J at-0.1V for devices with polymer PANT2 as active layer sc 5.8X10 -9 mA/cm 2 。
Furthermore, the results of the study obtained confirm that: the polymer containing the naphtho-bipyrazine-bisindene heterocyclic unit shown in the formula (I) provided by the invention is a conjugated polymer with excellent comprehensive performance; the polymer semiconductor material has large coplanar skeleton, strong heteroatom action and good solution processing property. The preparation method provided by the invention has the advantages of simplicity, effectiveness, easy availability of raw materials, strong popularization and the like. By changing different dissolution-assisting alkyl chains, heteroatom substitution and copolymerization units, a series of polymer materials containing naphthyridin bisindene heterocyclic units with excellent comprehensive performance can be prepared, which has very important significance for researching the internal correlation between the structure and the performance of a polymer semiconductor and has guiding significance for developing ultra-low band gap conjugated polymers with high performance in future.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. A class of polymers comprising a naphthyridobiindene heterocyclic unit, characterized in that the class of polymers comprising a benzobispyrazinodiindene heterocyclic unit has the structural formula of formula I or formula II:
Figure QLYQS_1
Figure QLYQS_2
in the formula I and the formula II, R is a straight-chain alkyl group with the total number of carbon atoms being 6-16 or a branched-chain alkyl group with the total number of carbon atoms being 8-30;
ar is one of the structures shown below, wherein R in Ar is as defined for R in formula I and formula II;
Figure QLYQS_3
in the formula I and the formula II, n is an integer of 10-300.
2. The polymer containing naphtho-bipyrazino-bisindene heterocyclic units according to claim 1, wherein the straight-chain alkyl group with the total number of carbon atoms being 6-16 is specifically: n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl;
the branched alkyl group having a total number of carbon atoms of 8 to 30 is specifically: 2-ethylhexyl, 2-hexyl-octyl, 4-hexyl-decyl, 3-hexyl-undecyl, 2-octyl-decyl, 2-octyl-dodecyl, 3-octyl-tridecyl, 2-decyl-dodecyl, 2-decyl-tetradecyl, 3-decyl-pentadecyl, 2-dodecyl-hexadecyl, 4-octyl-tetradecyl, 4-decyl-hexadecyl, 4-octyl-dodecyl, 4-decyl-tetradecyl or 4-dodecyl-hexadecyl.
3. The class of polymers containing a naphthyridobipyrazinodiindene heterocyclic unit according to claim 1, wherein the class of polymers containing a benzobispyrazinodiindene heterocyclic unit is PNAT1, the PNAT1 having the formula III:
Figure QLYQS_4
in the formula III, n is an integer of 10 to 300.
4. A class of polymers containing a naphthyridobipyrazinodiindene heterocyclic unit according to claim 1, wherein the class of polymers containing a benzobispyrazinodiindene heterocyclic unit is PNAT2, the PNAT2 having the formula IV:
Figure QLYQS_5
in the formula IV, n is an integer of 10 to 300.
5. A process for the preparation of a class of polymers containing naphthalazinobiindene heterocyclic units as claimed in any of claims 1 to 4, characterised in that it comprises the steps of:
s1, mixing 2-tributyltin-4-alkylthiophene with 5, 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole and carrying out palladium catalysis Stille coupling reaction to obtain an intermediate a;
s2, selectively reducing the intermediate a by using reduced zinc powder to obtain an intermediate b;
s3, carrying out condensation reaction on the intermediate b and ninhydrin hydrate to obtain an intermediate c or an intermediate d;
s4, carrying out nucleophilic substitution reaction on the intermediate c or the intermediate d under the action of malononitrile to obtain a compound e and a compound f respectively;
s5, performing electrophilic substitution reaction on the compound e or the compound f and N-bromosuccinimide to obtain a compound M respectively 1 And compound M 2 ，
S6, subjecting the compound M 1 Or a compound M 2 And bis (trimethyltin group) substituted aromatic heterocyclic monomer g are subjected to Stille coupling condensation reaction under the action of palladium catalyst to obtain polymerization containing benzodipyrazine bisindene heterocyclic units with structural formulas I and II respectivelyA material;
wherein the structural formula of the intermediate a is as follows:
Figure QLYQS_6
；
the structural formula of the intermediate b is as follows:
Figure QLYQS_7
;
the structural formula of the intermediate c is as follows:
Figure QLYQS_8
;
the structural formula of the intermediate d is as follows:
Figure QLYQS_9
;
the structural formula of the compound e is as follows:
Figure QLYQS_10
；
the structural formula of the compound f is as follows:
Figure QLYQS_11
；
the compound M 1 The structural formula is as follows:
Figure QLYQS_12
；
the compound M 2 The structural formula is as follows:
Figure QLYQS_13
；
the structural formula of the bis (trimethyltin group) -substituted aromatic heterocyclic monomer g is as follows:
Figure QLYQS_14
wherein R is a straight-chain alkyl group with the total number of carbon atoms of 6-16 or a branched-chain alkyl group with the total number of carbon atoms of 8-30;
ar is one of the structures shown below, wherein R in Ar is as defined for R in formula I and formula II;
Figure QLYQS_15
and n is an integer of 10-300.
6. The method according to claim 5, wherein,
the S1 specifically comprises the following steps: mixing 2-tributyltin-4-alkylthiophene, 5, 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole, palladium catalyst and solvent under the protection of nitrogen, and refluxing and stirring for 3-10 hours to obtain an intermediate a; the mass ratio of the 5, 10-dibromonaphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole, 2-tributyltin-4-alkyl thiophene and the palladium catalyst is 1.0:2.0-3.0:0.01-0.1;
the step S2 is specifically as follows: under the protection of nitrogen, mixing the intermediate a, the reduced zinc powder and the solvent, and refluxing and stirring for 3-10 hours to obtain an intermediate b;
the step S3 is specifically as follows: adding the intermediate b and ninhydrin into a solvent, mixing, refluxing and stirring for 1-3 hours, and cooling to obtain an intermediate c and an intermediate d; the mass ratio of the compound b to the ninhydrin is 1.0:3.0-10.0;
the step S4 specifically comprises the following steps: sequentially adding an intermediate c or an intermediate d, malononitrile, methylene dichloride and pyridine into a three-mouth bottle under the protection of nitrogen, slowly adding titanium tetrachloride, and stirring and reacting for 10-20 hours at 40 ℃ to obtain a compound e and a compound f respectively; the mass ratio of the intermediate c or the intermediate d to pyridine and malononitrile is 1.0:4.0-10.0:0.5-1.0;
the step S5 specifically comprises the following steps: mixing the compound e or the compound f with a solvent under the protection of nitrogen; then adding N-bromosuccinimide into the mixed solution, stirring and reacting for 5-10 hours at room temperature to respectively obtain a compound M 1 And compound M 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the compound e or the compound f to the N-bromosuccinimide is 1:2.0-3.0;
the step S6 specifically comprises the following steps: subjecting the compound M 1 Or a compound M 2 Mixing bis (trimethyltin group) substituted aromatic heterocyclic monomer g, a solvent and a palladium catalyst, and stirring and reacting for 24-72 hours at 80-150 ℃ under the protection of nitrogen to obtain a polymer containing naphtho-bipyrazino-bisindene heterocyclic units; the mass ratio of the compound M1 or M2, the bis (trimethyltin group) substituted aromatic heterocyclic monomer g and the palladium catalyst is 1:1.0-1.5:0.01-0.1.
7. The method of preparation of claim 6, wherein the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium;
the solvent is one or more of toluene, xylene, N-dimethylformamide, N-dimethylacetamide, chlorobenzene, dichlorobenzene, trichlorobenzene and tetrahydrofuran.
8. Use of a class of polymeric materials containing naphthacenedi-pyrazinodiindene heterocyclic units according to claim 1 in the preparation of organic photodetectors.
9. Use of a class of polymer materials containing naphtho-bipyrazino-bisindene heterocyclic units according to claim 8 for the preparation of an organic photodetector, comprising the steps of: an active layer is made of a class of polymer materials containing naphtho-bispyrazino-bisindene heterocyclic units and an electron donor material, wherein the molar ratio of the class of polymer materials containing naphtho-bispyrazino-bisindene heterocyclic units to the electron donor material is 1-1.5:1, and then the active layer is used in an organic photodetector device.
10. Use of a class of polymer materials containing naphtho-bipyrazino-bisindene heterocyclic units according to claim 9 for the preparation of an organic photodetector, characterized in that the electron donor material is an organic electron donor material; the electron donor material is at least one of PCE10, PCE12 and P3 HT:
Figure QLYQS_16
。/>
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