CN115028812A - Polymers containing naphtho-dipyrazinyl-diindene heterocyclic unit and preparation method and application thereof - Google Patents

Polymers containing naphtho-dipyrazinyl-diindene heterocyclic unit and preparation method and application thereof Download PDF

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CN115028812A
CN115028812A CN202210724907.7A CN202210724907A CN115028812A CN 115028812 A CN115028812 A CN 115028812A CN 202210724907 A CN202210724907 A CN 202210724907A CN 115028812 A CN115028812 A CN 115028812A
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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-dipyrazinediindene heterocyclic units, a preparation method and application thereof. The polymer containing the naphtho-bipyrazindine-indene heterocyclic unit takes the naphtho-bipyrazindine-indene heterocyclic as an acceptor unit, and the polymer material prepared from the naphtho-bipyrazindine-indene heterocyclic unit has good solubility, film-forming property and thermal stability, can be applied to preparation of organic photodetector devices, shows the characteristic of low dark current, and has wide commercial prospect in the fields of organic electronic devices, biomedical images and the like.

Description

Polymers containing naphtho-dipyrazinyl-diindene heterocyclic unit 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-dipyrazinyl-bisindenyl heterocyclic unit, and a preparation method and application thereof.
Background
The ultralow band gap conjugated polymer has the advantages of extremely small optical band gap (<1.0eV), high electron affinity, low ionic potential, ultra-wide spectrum corresponding characteristics (the 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 detectors, near infrared electrochromic devices, near infrared biological imaging and the like. The research shows that: the optical band gap of the polymer can be remarkably reduced by adopting an alternating copolymerization mode of an acceptor (A) unit with strong electricity shortage and a donor (D) unit with strong electricity enrichment, and a D-A type ultralow band gap conjugated polymer can be constructed. Currently, acceptor building units for ultra-low bandgap conjugated polymers are mainly concentrated in thiazole and pyrazine ring heterocyclic acceptor units, such as benzodithiadiazole (BBT, j.am.chem.soc.,2011,133,20799), thienopyrazines (TP, chem.commun.,2011,47,11394), thienothiazoles (TTZ, appl.phys.lett.,2006,89,081106), compared to donor (D) units of strong electrical rich properties. Therefore, receptor building units which can be used for constructing the ultralow-band-gap conjugated polymer are scarce, which also draws extensive attention of a plurality of researchers. In order to solve the problem of scarcity of the strong electron-deficient units, it is of great significance to further develop novel strong electron-deficient receptor units and ultralow band gap conjugated polymers thereof.
Disclosure of Invention
The invention provides a polymer containing naphtho-bipyrazindine-indene heterocyclic unit, a preparation method and application thereof, aiming at the challenges of few types of ultralow band gap conjugated polymer materials, scarce receptor building units, high dark current density and the like.
In order to solve the technical problems, the invention provides a polymer containing a naphtho-bipyrazindine heterocyclic unit, wherein the polymer containing the naphtho-bipyrazindine heterocyclic unit has a structural formula shown in the following formula I or formula II:
Figure BDA0003712931220000011
Figure BDA0003712931220000021
in the formula I and the formula II, R is linear alkyl with 6-16 carbon atoms in total or branched alkyl with 8-30 carbon atoms in total;
ar is one of the structures shown below, but is not limited to the following structural formula, wherein R in Ar is defined as the same as R in formula I and formula II;
Figure BDA0003712931220000022
in the formula I and the formula II, n is an integer of 10-300.
Preferably, the linear alkyl groups with the total number of carbon atoms of 6-16 are: 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 with the total carbon atom number of 8-30 specifically comprises the following components: 2-ethylhexyl group, 2-butylhexyl group, 2-hexyloctyl group, 4-hexyldecyl group, 3-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 3-octyltridecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-decylpentadecyl group, 2-dodecylhexadecyl group, 4-octyltetradecyl group, 4-decylcetyl group, 4-hexyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group or 4-dodecylhexadecyl group; n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl.
Preferably, the polymer containing the naphthopyrazinediindene heterocyclic unit is PNAT1, and the PNAT1 has the following structural formula III:
Figure BDA0003712931220000031
in the formula III, n is an integer of 10-300.
Preferably, the type of polymer containing naphthopyrazinediindane heterocyclic unit is PNAT2, wherein PNAT2 has the following formula IV:
Figure BDA0003712931220000032
in the formula IV, n is an integer of 10-300.
As a general technical concept, the present invention also provides a method of preparing the above-mentioned polymer containing naphthopyrazinodiindene heterocyclic units, 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-catalyzed 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 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 respectively obtain a compound e and a compound f;
s5, carrying out electrophilic substitution reaction on the compound e or the compound f and N-bromosuccinimide to obtain a compound M 1 And a compound M 2 ，
S6, mixing the compound M 1 Or compounds M 2 Performing Stille coupling condensation reaction with a bis-methyl tin group substituted aromatic heterocyclic monomer g under the action of a palladium catalyst to respectively obtain polymers containing benzodipyrazino-biindane heterocyclic units with structural formulas of a formula I and a formula 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 of (A) is:
Figure BDA0003712931220000053
the compound M 2 The structural formula of (A) is:
Figure BDA0003712931220000061
the structural formula of the bis-methyl tin group substituted aromatic heterocyclic monomer g is as follows:
Figure BDA0003712931220000062
wherein R is a linear alkyl group with 6-16 carbon atoms in total or a branched alkyl group with 8-30 carbon atoms in total;
ar is one of the structures shown below, but is not limited to the following structural formula, wherein R in Ar is defined as the same as R in formula I and formula II;
Figure BDA0003712931220000063
and n is an integer of 10-300.
In the above preparation method, preferably, S1 specifically is: under the protection of nitrogen, mixing 2-tributyltin-4-alkylthiophene, 5, 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole, a palladium catalyst and a solvent, and carrying out reflux 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 to the 2-tributyltin-4-alkylthiophene to the palladium catalyst is 1.0: 2.0-3.0: 0.01-0.1;
in the preparation method, preferably, the S2 is specifically: under the protection of nitrogen, mixing the intermediate a, the reduced zinc powder and a solvent, and carrying out reflux stirring for 3-10 hours to obtain an intermediate b;
in the above preparation method, preferably, S3 specifically is: adding the intermediate b and ninhydrin into a solvent for 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 preparation method, preferably, the S4 is specifically: under the protection of nitrogen, mixing the intermediate c or the intermediate d, malononitrile, dichloromethane and pyridine, finally slowly adding titanium tetrachloride, stirring and reacting for 10-20 hours at 40 ℃ to respectively obtain a compound e and a compound f; 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, S5 specifically is: under the protection of nitrogen, mixing the compound e or the compound f with a solvent; 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 a compound M 2 (ii) a The compound e or the compound f and N-The mass ratio of bromosuccinimide is 1: 2.0-3.0;
in the preparation method, preferably, the S6 is specifically: subjecting said compound M to 1 Or compounds M 2 Mixing the bis-methyl tin 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 naphtho-bipyrazinyl biindenyl heterocyclic unit; the mass ratio of the compound M1 or M2, the bis-methyl tin 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 naphtho-dipyrazinyl-bisindenyl heterocyclic unit in preparation of an organic photoelectric detector device.
The application specifically comprises the step of preparing a polymer material containing a naphtho-dipyrazinyl heterocycle unit and an electron donor material into an active layer, wherein the molar ratio of the polymer containing the naphtho-dipyrazinyl heterocycle 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 naphtho-dipyrazinyl-bisindane heterocyclic unit has the advantages of strong universality of a synthetic method, mild synthetic conditions, high synthetic yield and the like, and can be popularized and applied to large-scale synthesis and production in industry;
(2) the polymer material containing the naphtho-bipyrazindine-indene heterocyclic unit provided by the invention has a large pi conjugated skeleton of hetero atoms, can enhance the pi-pi interaction in molecules and among molecules, and improves the carrier mobility;
(3) the polymer material containing the naphtho-dipyrazinediindene heterocyclic unit provided by the invention has a lower HOMO energy level due to the introduction of the electron-deficient receptor unit;
(4) the polymer material containing the naphtho-dipyrazinyl-indene heterocyclic unit has wide commercial prospect in the organic electronic field such as an organic photodetector;
(7) the polymer material containing the naphtho-dipyrazinyl-indene heterocyclic unit provided by the invention is used as an active layer of a device, and the dark current density of an organic photodetector of the polymer material is 10 -7 mA/cm 2 The advantages of a class of polymeric materials containing naphthopyrazinodiindene heterocyclic units are fully demonstrated below.
Drawings
FIG. 1 is an absorption spectrum of a solid film of a polymer material PAN1 containing naphthopyrazinediindene heterocyclic units, which is prepared in example 1, in a chloroform solution and a quartz plate;
FIG. 2 is an absorption spectrum of a solid film of a polymer material PANT2 containing a naphthopyrazinodiindene heterocyclic unit prepared in example 2 in a chloroform solution and a quartz plate;
FIG. 3 is a schematic structural diagram of an organic photodetector device using polymer materials PANT1 and PANT2 containing naphthopyrazinodiindene heterocyclic units prepared in examples 1 and 2 as organic active layers;
FIG. 4 is a J-V curve of an organic photodetector using the polymer materials PANT1 and PANT2 containing naphthopyrazinodiindene heterocyclic units prepared in examples 1 and 2 as organic active semiconductor layers;
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The examples described below are intended to facilitate the understanding of the invention without having any limiting effect thereon. The method is a conventional method unless otherwise specified. The reaction mass can be purchased from a publicly available commercial source unless otherwise specified.
Example 1:
the invention relates to a polymer PNAT1 containing naphtho-dipyrazinediindene heterocyclic unit, wherein the PNAT1 has a structural general formula as shown in 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, 2-tributyltin-4-decylthiophene (6.22mmol), 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole (2.49mmol), bis (triphenylphosphine) palladium dichloride (0.25mmol), and 50mL of toluene solvent were added under nitrogen. After stirring under reflux for 3 hours, the reaction was cooled to room temperature. And extracting an organic phase by using dichloromethane and saturated salt water, drying the organic phase by using anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. Purifying with silica gel column chromatography (eluent petroleum ether: dichloromethane: 5:1, V: V) to obtain intermediate a as red solid (yield: 82%).
The structural characterization data of the intermediate a is 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 compound has a correct structure and is the intermediate a shown.
(2) And (3) synthesis of an intermediate c: intermediate a (1.45mmol), reduced zinc powder (43.54mmol) and 30mL of acetic acid solvent were added to a three-necked flask under nitrogen. After stirring under reflux for 5 hours, the reaction was cooled to room temperature. And (3) filtering redundant zinc powder, extracting an organic phase by using ethyl acetate, drying by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain an amine compound intermediate b.
Then, the amine intermediate b and ninhydrin (5.75mmol) were added to a three-necked flask containing 20mL of ethanol solution to react, and after stirring at reflux for 12 hours, the reaction mixture was cooled to room temperature. Extracting with dichloromethane, drying with anhydrous magnesium sulfate, spin-drying the solvent under reduced pressure, and purifying with silica gel column chromatography (eluent petroleum ether: dichloromethane: 2: 1, V: V) to obtain green solid, i.e. intermediate c (yield: 45%).
Intermediate c structural 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 compound has a correct structure and is the intermediate c shown.
(3) And (3) synthesis of an intermediate e: to a three-necked flask, under nitrogen, was added the intermediate c (1.13mmol), malononitrile (5.67mmol), 50mL of dichloromethane, and 3mL of pyridine in that order, and finally 0.5mL of titanium tetrachloride was added slowly. 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, spin-drying the solvent under reduced pressure, and purifying the obtained crude product with silica gel chromatography column (eluent petroleum ether: dichloromethane: 2: 1, V: V) to obtain dark brown solid, i.e. intermediate e (yield: 82%).
The structural characterization data of the intermediate e 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 compound has a correct structure and is the intermediate e shown.
(4) Compound M 1 The synthesis of (2): under nitrogen, intermediate e (1.02mmol) was added to a three-necked flask containing chloroform and N, N' -dimethylformamide, and the mixture was stirred in an ice bath. Then, N-bromosuccinimide (2.25mmol) was dissolved in 5mL of N, N' -dimethylformamide to obtain a mixed solution, and the mixed solution was slowly added dropwise to the reaction solution using a syringe. After stirring the reaction mixture at room temperature for 12 hours, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. Purifying the crude product with silica gel chromatography column (eluent petroleum ether: dichloromethane: 2: 1, V: V) to obtain brown solid as 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。
as can be seen from the above, the compound has the correct structure and is the compound M 1 。
(5) Synthesis of Polymer PNA 1: monomer Compound M 1 (0.176mmol), 2, 5-bis (trimethyltin) thiophene (0.352mmol), 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 mixture is stirred and reacted for 72 hours at the temperature of 115 ℃ under the protection of nitrogen, and then cooled to room temperature. Adding 200mL of methanol, stirring at room temperature for 0.5h, carrying out suction filtration, and loading the obtained polymer into a Soxhlet extractor for extraction. 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, i.e. PNAT1 (yield: 90%).
The molecular weights and their molecular weight distributions are as follows: weight average molecular weight M w 29.9kDa, number average molecular weight M n 13.1kDa and a polymer molecular weight distribution index of 2.25.
Example 2:
the invention relates to a polymer PNAT2 containing naphtho-dipyrazinediindene heterocyclic unit, wherein the PNAT2 has a structural general formula shown in a 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 according to the synthesis method described above in example 1.
(2) Synthesis of intermediate d: intermediate a (1.45mmol), reduced zinc powder (43.54mmol) and 30mL of acetic acid solvent were added to a three-necked flask under nitrogen. After stirring under reflux for 5 hours, the reaction was cooled to room temperature. And (3) filtering redundant zinc powder, extracting an organic phase by using ethyl acetate, drying by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain an amine compound intermediate b. Then, the amine intermediate b and ninhydrin (5.75mmol) were added to a three-necked flask containing 20mL of ethanol solution to react, and after stirring at reflux for 12 hours, the reaction mixture was cooled to room temperature. Extracting with dichloromethane, drying with anhydrous magnesium sulfate, spin-drying the solvent under reduced pressure, and purifying with silica gel column chromatography (eluent petroleum ether: dichloromethane: 2: 1, V: V) to obtain dark green solid, i.e. intermediate d (yield: 35%).
Intermediate d structural 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 compound has a correct structure and is the intermediate d shown.
(3) And (3) synthesis of an intermediate f: to a three-necked flask, under nitrogen, was added the intermediate c (1.13mmol), malononitrile (5.67mmol), 50mL of dichloromethane, and 3mL of pyridine in that order, and finally 0.5mL of titanium tetrachloride was added slowly. 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, spin-drying the solvent under reduced pressure, and purifying the crude product with silica gel chromatography column (eluent petroleum ether: dichloromethane: 2: 1, V: V) to obtain brown solid, i.e. intermediate e (yield: 75%).
Intermediate e structural 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 compound has a correct structure and is the intermediate f shown.
(4) Compound M 2 The synthesis of (2): under nitrogen, intermediate e (1.02mmol) was added to a three-necked flask containing chloroform and N, N' -dimethylformamide, and the mixture was stirred in an ice bath. Then, N-bromosuccinimide (2.25mmol) 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 using a syringe. After stirring the reaction mixture at room temperature for 12 hours, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. Purifying the crude product with silica gel chromatography column (eluent petroleum ether: dichloromethane: 2: 1, V: V) to obtain brown solid as 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。
as can be seen from the above, the compoundWith correct structure, is the shown compound M 2 。
(5) Synthesis of Polymer PNA 2: monomer Compound M 2 (0.176mmol), 2, 5-bis (trimethyltin) thiophene (0.352mmol), 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 mixture is stirred and reacted for 72 hours at the temperature of 115 ℃ under the protection of nitrogen, and then cooled to room temperature. Adding 200mL of methanol, stirring at room temperature for 0.5h, carrying out suction filtration, and loading the obtained polymer into a Soxhlet extractor for extraction. 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, i.e. PNAT2 (yield 80%).
The molecular weights and their molecular weight distributions are as follows: weight average molecular weight M w 39.9kDa, number average molecular weight M n 20.1kDa and a polymer molecular weight distribution index of 1.98.
Determination of spectral properties and organic photodetector properties of a class of polymers PANT1 and PANT2 containing naphthopyrazinodiindene heterocyclic units prepared in examples 1 and 2 above:
(1) absorption spectrum property of polymer PANT1 containing naphtho-dipyrazinyl-indene heterocyclic unit
FIG. 1 shows UV-VIS-NIR absorption spectra of a class of polymers PANT1 containing naphthopyrazinodiindene heterocyclic units in chloroform solution and a thin film on a quartz plate (the thin film is prepared by spin-coating chloroform solution on the quartz plate). As can be seen from FIG. 1, a class of solutions and films of the polymer PANT1 containing naphthopyrazinodiindene heterocyclic units exhibit a wide absorption range, the absorption maximum absorption side band values of the films are all around 1266nm, and the corresponding optical band gaps are 0.98eV (the optical band gaps are according to the formula E) g 1240/λ calculation, where E g Is the optical band gap and lambda is the absorption maximum side band value of the film).
(2) Absorption spectrum property of polymer PANT2 containing naphtho-dipyrazinyl-indene heterocyclic unit
FIG. 2 shows a class of polymers PANT2 containing naphthopyrazinodiindene heterocyclic units in chloroform solution and on quartz slidesUltraviolet-visible-near infrared absorption spectra of thin films (thin films prepared by spin coating chloroform solution on quartz plates). As can be seen from FIG. 2, a class of solutions and films of the polymer PANT2 containing naphthopyrazinodiindene heterocyclic units exhibit a wide absorption range, the absorption maximum absorption side band values of the films are all about 1294nm, and the corresponding optical band gaps are 0.96eV (the optical band gaps are according to the formula E) g 1240/λ calculation, where E g Is the optical band gap and lambda is the absorption maximum side band value of the film).
(3) Organic photodetector Performance measurements of polymers PANT1 and PANT2
The invention adopts the device structure shown in figure 3 to research the semiconductor characteristics of the polymer film in the organic photodetector. The device preparation method comprises the following steps: taking Indium Tin Oxide (ITO) glass with the square resistance of 10 omega, sequentially using acetone, a detergent, deionized water and isopropanol for ultrasonic cleaning, and carrying out plasma treatment for 10 minutes; spin-coating a poly-ethoxy-thiophene (PEDOT: PSS ═ 1:6, w/w) film doped with polystyrene sulfonic acid on ITO, drying the PEDOT: PSS film with a thickness of 30nm in a vacuum oven at 80 ℃ for 8 hours; then a chlorobenzene solution (2 wt.%) of polymer: PC71BM ═ 1:1.5w/w was spin coated on the surface of PEDOT: PSS film to a thickness of 100nm as an active layer; and 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, wherein the device structure is as follows: ITO/PEDOT: PSS/polymer: PC71 BM/Ca/Al. The test results are shown in fig. 4: dark current J at-0.1V for devices with polymer PANT1 as the active layer sc Is 1.4X 10 -8 mA/cm 2 (ii) a Dark current J at-0.1V for devices with polymer PANT2 as the active layer sc Is 5.8 multiplied by 10 -9 mA/cm 2 。
Furthermore, the results of the study obtained confirm that: the polymer containing the naphtho-dipyrazinyl-indene heterocyclic unit shown in the formula (I) is a conjugated polymer with excellent comprehensive performance; the polymer semiconductor material has large coplanar framework, strong heteroatom effect and good solution processability. The preparation method provided by the invention has the advantages of simplicity, effectiveness, easily available raw materials, strong popularization and the like. By changing different cosolvent alkyl chains and heteroatom substitution and copolymerization units, a series of polymer materials containing naphtho-bipyrazindine heterocyclic units with excellent comprehensive performance can be prepared, which has very important significance for researching the internal relation between the structure and the performance of a polymer semiconductor and has guiding significance for developing high-performance ultralow band gap conjugated polymers in the future.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A class of polymers containing a naphthopyrazinodiindene heterocyclic unit is characterized in that the class of polymers containing the benzodipyrazinodiindene heterocyclic unit has a structural formula I or II as follows:
Figure FDA0003712931210000011
in the formula I and the formula II, R is a straight-chain alkyl group with 6-16 carbon atoms in total or a branched-chain alkyl group with 8-30 carbon atoms in total;
ar is one of the structures shown below, but is not limited to the following structural formula, wherein R in Ar is defined as the same as R in formula I and formula II;
Figure FDA0003712931210000012
in the formula I and the formula II, n is an integer of 10-300.
2. The polymer containing naphthopyrazinediindene heterocyclic units according to claim 1, wherein the straight-chain alkyl groups with the total number of carbon atoms of 6 to 16 are 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 with the total carbon atom number of 8-30 specifically comprises the following components: 2-ethylhexyl group, 2-butylhexyl group, 2-hexyloctyl group, 4-hexyldecyl group, 3-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 3-octyltridecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-decylpentadecyl group, 2-dodecylhexadecyl group, 4-octyltetradecyl group, 4-decylcetyl group, 4-hexyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group or 4-dodecylhexadecyl group; n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl.
3. A class of polymers containing a naphthopyrazinobindane heterocyclic unit according to claim 1, wherein said class of polymers containing a benzodipyrazinobindane heterocyclic unit is PNAT1, said PNAT1 has the formula III:
Figure FDA0003712931210000021
in the formula III, n is an integer of 10-300.
4. The class of polymers comprising naphthopyrazinediindane heterocyclic units according to claim 1, wherein said class of polymers comprising benzodipyrazinediindane heterocyclic units is PNAT2, said PNAT2 having the formula IV:
Figure FDA0003712931210000022
in the formula IV, n is an integer of 10-300.
5. A method for preparing the polymer containing the naphthopyrazinediindene heterocyclic unit according to any one of claims 1 to 4, which comprises the following steps:
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-catalyzed 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 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 respectively obtain a compound e and a compound f;
s5, carrying out electrophilic substitution reaction on the compound e or the compound f and N-bromosuccinimide to obtain a compound M 1 And a compound M 2 ，
S6, mixing the compound M 1 Or compounds M 2 Performing Stille coupling condensation reaction with a bis-methyl tin group substituted aromatic heterocyclic monomer g under the action of a palladium catalyst to respectively obtain polymers containing benzodipyrazino-biindane heterocyclic units with structural formulas of a formula I and a formula II;
wherein the structural formula of the intermediate a is as follows:
Figure FDA0003712931210000031
the structural formula of the intermediate b is as follows:
Figure FDA0003712931210000032
the structural formula of the intermediate c is as follows:
Figure FDA0003712931210000033
the structural formula of the intermediate d is as follows:
Figure FDA0003712931210000041
the structural formula of the compound e is as follows:
Figure FDA0003712931210000042
the structural formula of the compound f is as follows:
Figure FDA0003712931210000043
the compound M 1 The structural formula of (A) is:
Figure FDA0003712931210000051
the compound M 2 The structural formula of (A) is:
Figure FDA0003712931210000052
the structural formula of the bis-methyl tin group substituted aromatic heterocyclic monomer g is as follows:
Figure FDA0003712931210000053
wherein R is a linear alkyl group with 6-16 carbon atoms in total or a branched alkyl group with 8-30 carbon atoms in total;
ar is one of the structures shown below, but is not limited to the following structural formula, wherein R in Ar is the same as the definition of R in formula I and formula II;
Figure FDA0003712931210000054
and n is an integer of 10-300.
6. The production method according to claim 5,
the S1 specifically includes: under the protection of nitrogen, mixing 2-tributyltin-4-alkylthiophene, 5, 10-dibromo-naphtho [1,2-c:5,6-c' ] bis [1,2,5] thiadiazole, a palladium catalyst and a solvent, and carrying out reflux 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 to the 2-tributyltin-4-alkylthiophene to the palladium catalyst is 1.0: 2.0-3.0: 0.01-0.1;
the S2 specifically includes: under the protection of nitrogen, mixing the intermediate a, the reduced zinc powder and a solvent, and carrying out reflux stirring for 3-10 hours to obtain an intermediate b;
the S3 specifically includes: adding the intermediate b and ninhydrin into a solvent for 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 S4 specifically includes: under the protection of nitrogen, sequentially adding the intermediate c or the intermediate d, malononitrile, dichloromethane and pyridine into a three-necked bottle, finally slowly adding titanium tetrachloride, and stirring and reacting at 40 ℃ for 10-20 hours to respectively obtain a compound e and a compound f; 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 S5 specifically includes: under the protection of nitrogen, mixing the compound e or the compound f with a solvent; 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 a compound M 2 (ii) a The mass ratio of the compound e or the compound f to the N-bromosuccinimide is 1: 2.0-3.0;
the S6 specifically includes: subjecting said compound M to 1 Or compounds M 2 Bis (methyl tin) substituted heteroaromatic monomer g, solvent and palladium catalystMixing the reagents, and stirring and reacting at 80-150 ℃ for 24-72 hours under the protection of nitrogen to obtain a polymer containing a naphtho-bipyrazinyl biindenyl heterocyclic unit; the mass ratio of the compound M1 or M2, the bis-methyl tin group substituted aromatic heterocyclic monomer g and the palladium catalyst is 1: 1.0-1.5: 0.01-0.1.
7. The production method according to 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. The use of a class of naphthopyrazinediindene heterocyclic unit-containing polymeric materials according to claim 1 in the preparation of organic photodetectors.
9. The application of the polymer containing the naphthopyrazinediindene heterocyclic unit in the preparation of the organic photodetector according to claim 8, is characterized by comprising the following steps: a polymer material containing a naphtho-dipyrazinyl heterocyclic unit and an electron donor material are prepared into an active layer, the molar ratio of the polymer containing the naphtho-dipyrazinyl heterocyclic unit to the electron donor material is 1-1.5:1, and then the active layer is used in an organic photodetector device.
10. The application of the polymer material containing the naphthopyrazinobiindane heterocyclic unit in the preparation of the organic photodetector according to claim 9, wherein 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 FDA0003712931210000071
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108948327A (en) * 2017-05-19 2018-12-07 中国科学院化学研究所 A kind of quinoxaline conjugated polymer and preparation method thereof and its application in polymer solar cells
CN110128631A (en) * 2019-02-18 2019-08-16 湘潭大学 Super low band-gap conjugated polymer of D-A type and the preparation method and application thereof
CN113793905A (en) * 2014-09-26 2021-12-14 Udc 爱尔兰有限责任公司 Fluorescent organic light emitting element with high efficiency

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113793905A (en) * 2014-09-26 2021-12-14 Udc 爱尔兰有限责任公司 Fluorescent organic light emitting element with high efficiency
CN108948327A (en) * 2017-05-19 2018-12-07 中国科学院化学研究所 A kind of quinoxaline conjugated polymer and preparation method thereof and its application in polymer solar cells
CN110128631A (en) * 2019-02-18 2019-08-16 湘潭大学 Super low band-gap conjugated polymer of D-A type and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CUNBIN AN等: "Thiadizoloquinoxaline-Based Low-Bandgap Conjugated Polymers as Ambipolar Semiconductors for Organic Field Effect Transistors", 《CHEMISTRY OF MATERIALS》 *

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