A y-based organic semiconductor material containing intrinsic chirality, and a preparation method and application thereof

Abstract

The application belongs to the technical field of photoelectric functional materials, and particularly relates to a Y-based organic semiconductor material containing intrinsic chirality and a preparation method and application. The Y-based organic semiconductor material containing intrinsic chirality provided in the application creatively introduces a chiral side chain into a dithiophene beta position of a Y-based non-fullerene acceptor molecule in a preparation process, simultaneously introduces chiral alkyl side chains into the dithiophene beta position and a pyrrole N position, has four chiral sites, can realize high circular dichroism absorption and light emission characteristics, and has a low HOMO energy level, which is beneficial to realizing efficient charge transport and photo-generated carrier migration. When used as an active layer material of a photoelectric device, the Y-based organic semiconductor material can make the chiral asymmetric response of the photoelectric device good, and prepare a low-power-consumption and high-selectivity photoelectric device, and is a high-performance Y-based organic semiconductor material. Thus, the technical problem of lack of high-performance Y-based organic semiconductor materials in the prior art is solved.

Description

Technical Field

[0001] This application belongs to the field of optoelectronic functional materials technology, and in particular relates to a Y-based organic semiconductor material with intrinsic chirality, its preparation method and application. Background Technology

[0002] The circularly polarized light absorption and emission properties of optoelectronic functional materials play a crucial role in advanced applications such as quantum optics, secure communication, and imaging, and can be used as active layer materials for optoelectronic devices such as circularly polarized light detectors and circularly polarized light-emitting diodes.

[0003] In traditional optoelectronic functional materials, inorganic semiconductor materials such as silicon and indium gallium arsenide lack intrinsic chirality. This necessitates the additional configuration of optical components such as linear polarizers and quarter-wave plates in conventional circularly polarized light-emitting diodes (LEDs) and circularly polarized light detectors to indirectly identify circularly polarized light. The configuration of these optical components increases device costs and hinders chip integration. In contrast, organic semiconductor materials possess advantages such as high absorption coefficients, tunable band gaps, good flexibility, and low cost. Furthermore, through precise molecular design and chiral engineering, organic semiconductor materials containing intrinsic chirality can be fabricated, enabling the emission and response of polarized light without the need for optical components such as linear polarizers and quarter-wave plates. This provides a new approach and method to overcome the limitations of traditional polarized light detectors and circularly polarized LEDs.

[0004] Dithienothienopyrrolobenzothiadiazole (BTP), an organic semiconductor material, possesses advantages such as good chemical stability and strong modifiability. Y-based non-fullerene acceptors based on BTP have low HOMO energy levels, which is beneficial for achieving efficient charge transport and photogenerated carrier migration, exhibiting excellent optoelectronic performance in optoelectronic devices such as organic photovoltaics, organic light-emitting diodes, and organic field-effect transistors. Furthermore, by modifying different sites, numbers, groups, or chiral side chains, the intermolecular interactions, charge transport capabilities, and circularly polarized light absorption properties of molecules can be more flexibly adjusted, greatly enriching the types of organic semiconductor materials and optimizing their performance. However, current research on chiral side chain modification is insufficient, and there is a lack of high-performance intrinsically chiral Y-based organic semiconductor materials, resulting in insufficient performance of optoelectronic devices such as circularly polarized light detectors. Therefore, it is necessary to develop novel high-performance intrinsically chiral Y-based organic semiconductor materials. Summary of the Invention

[0005] In view of this, this application provides an intrinsically chiral Y-based organic semiconductor material, its preparation method, and its application, in order to solve the technical problem of the lack of high-performance Y-based organic semiconductor materials in the prior art.

[0006] The first aspect of this application provides a Y-based organic semiconductor material with intrinsic chirality, whose general chemical formula is shown in Formula I; Formula I; In Formula I, R is a chiral alkyl side chain, and R1 is selected from at least one of hydrogen-based, aldehyde-based, and (2,3-dicyano-4-aryl-3-oxo-2,3-dihydro-1H-indene-1-yl) vinyl groups.

[0007] Preferably, R1 is selected from hydrogen-based materials, and the chemical structure of the intrinsically chiral Y-based organic semiconductor material is shown in Formula II; Formula II; In Formula II, R is selected from one of the following chiral alkyl side chains: .

[0008] Preferably, R1 is selected from aldehyde groups, and the chemical structure of the intrinsically chiral Y-based organic semiconductor material is shown in Formula III; Formula III; In Formula III, R is selected from one of the following chiral alkyl side chains: .

[0009] Preferably, R1 is selected from (2,3-dicyano-4-aryl-3-oxo-2,3-dihydro-1H-inden-1-yl) vinyl, and the chemical structure of the intrinsically chiral Y-based organic semiconductor material is shown in Formula IV; Formula IV; In Formula IV, R is selected from one of the following chiral alkyl side chains: ; In R1, Ar is selected from one of the following aryl groups: .

[0010] The second aspect of this application provides a method for preparing an intrinsically chiral Y-based organic semiconductor material, which can prepare the intrinsically chiral Y-based organic semiconductor material described in the first aspect, comprising the following steps: Oxidation step of chiral alkyl groups: Selective oxidation of primary alcohols in chiral alkyl alcohols to obtain chiral alkyl aldehydes; The steps of the nucleophilic addition reaction are as follows: a lithiumized solution containing a chiral alkyl aldehyde and 3-bromothiophene[3,2-b]thiophene undergoes a nucleophilic addition reaction of the carbonyl group to give the first intermediate product; The dehydroxylation step: The first intermediate is subjected to a dehydroxylation reaction using a dehydroxylation reagent to obtain the second intermediate; The steps of the cross-coupling reaction are as follows: After modifying the α-position of the olefin of the second intermediate with organotin, it is reacted with 4,7-dibromo-5,6-dinitrobenzothiadiazole via a Stille cross-coupling reaction to obtain the third intermediate. The steps of the nitro reduction reaction are as follows: the nitro group in the third intermediate is reduced to an amino group to obtain the nitro-reduced amination product of the third intermediate; The steps of the nucleophilic substitution reaction are as follows: the nitro-reduced amination product of the third intermediate and the chiral alkyl bromide are subjected to an SN2 nucleophilic substitution reaction of the amino group to obtain the intrinsically chiral Y-series organic semiconductor material.

[0011] Preferably, after the SN2 nucleophilic substitution reaction of the amino group, the reaction further includes: a formylation reaction sequentially with a lithiumized solution and N,N-dimethylformamide, followed by reactions with 2-(3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, 2-(5-chloro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, and 2-(4,5,6,7-tetrachloro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile. The following malononitrile, 2-(5-bromo-3-oxo-2,3-dihydro-1H-indene-1-ylidene) malononitrile, 2-(5,6-difluoro-1-naphthyl-3-oxo-2,3-dihydro-1H-indene-1-ylidene) malononitrile, 2-(5-methyl-3-oxo-2,3-dihydro-1H-indene-1-ylidene) malononitrile, 2-(4-oxo-4,5-dihydro-6H-cyclopentathiophene-6-ylidene) malononitrile, and 2-(3-chloro-6-oxo-5,6-dihydro-4H-cyclopentathiophene-4-ylidene) maleidonitrile undergoes a Knoevenagel condensation reaction.

[0012] Preferably, in the oxidation step of the chiral alkyl group, the oxidant used in the selective oxidation is selected from at least one mild oxidant among pyridine chlorochromate, pyridine chlorochromate, and Jones' reagent (an aqueous solution of chromium trioxide, sulfuric acid, and water in a certain proportion). The selective oxidation reaction was carried out at room temperature (20-30℃) for 2-6 hours.

[0013] Preferably, the chiral alkyl aldehyde is obtained by catalytic hydrogenation of a chiral alkyl alcohol containing an unsaturated carbon-carbon double bond, such as (S)-(+)-citronellol.

[0014] Preferably, in the nucleophilic addition reaction step, the nucleophilic addition reaction of the carbonyl group includes: under a protective atmosphere, cooling a solution of 3-bromothiophene[3,2-b]thiophene to -70~-85℃, adding n-butyllithium dropwise for 1~3h to obtain a lithiumized solution of 3-bromothiophene[3,2-b]thiophene, adding a chiral alkyl aldehyde, naturally heating to room temperature (20~30℃), stirring overnight (8~16h) to carry out the nucleophilic addition reaction of the carbonyl group.

[0015] Preferably, in the dehydroxylation step, the dehydroxylation reagent used in the dehydroxylation reaction is a solution of aluminum trichloride and lithium aluminum hydride; The dehydroxylation reaction was carried out at room temperature (20-30°C) for 8-16 hours overnight.

[0016] Preferably, in the cross-coupling reaction step, the reagents used for modifying organotin are: a tetrahydrofuran solution of lithium diisopropylaminodimethylamine and tri-n-butyltin chloride, and the reaction temperature for modifying organotin is room temperature (20~30℃), and the reaction time is overnight (8~16h). The stille cross-coupling reaction was carried out at a temperature of 110-120°C for 8-16 hours overnight.

[0017] Preferably, in the nitro reduction reaction step, the nitro reducing agent used is a triethyl phosphite solution, and the reaction temperature is 160~180℃, and the reaction time is overnight (8~16h).

[0018] Preferably, in the nucleophilic substitution reaction step, the base and activating agent used in the SN2 nucleophilic substitution reaction of the amino group are potassium carbonate and potassium iodide, and the reaction temperature is 70~90°C, and the reaction time is overnight (8~16h).

[0019] Preferably, in the formylation reaction, the lithiation solution is a n-butyllithium solution; The formylation reaction process includes: under a protective atmosphere, reacting the product of the SN2 nucleophilic substitution reaction of the amino group with a lithiumized solution at -70~-85℃ for 1~3h, then adding N,N-dimethylformamide and naturally heating to room temperature (20~30℃) and stirring overnight (8~16h) to carry out the formylation reaction.

[0020] Preferably, in the Knoevenagel condensation reaction, the alkaline catalyst used is pyridine, and the reaction temperature is 50~60℃, the time is 4~8h, and the atmosphere is a protective atmosphere.

[0021] Preferably, after the catalytic hydrogenation reaction, the selective oxidation, the nucleophilic addition reaction of the carbonyl group, the dehydroxylation reaction, the modification of organotin, the reduction of the nitro group to an amino group, the SN2 nucleophilic substitution reaction of the amino group, the formylation reaction, or the Knoevenagel condensation reaction, the post-processing includes: separating and / or purifying the target product from the reaction mixture.

[0022] Preferably, in the catalytic hydrogenation reaction, the selective oxidation, the nucleophilic addition reaction of the carbonyl group, the dehydroxylation reaction, the modification of organotin, the reduction of the nitro group to an amino group, the SN2 nucleophilic substitution reaction of the amino group, the formylation reaction, or the Knoevenagel condensation reaction, the solvent used is selected from at least one of ethyl acetate, chloroform, diethyl ether, tetrahydrofuran, toluene, and o-dichlorobenzene.

[0023] A third aspect of this application provides a circularly polarized light detector, wherein the active layer material comprises a Y-based organic semiconductor material with intrinsic chirality as described in the first aspect.

[0024] The fourth aspect of this application provides the application of the intrinsically chiral Y-based organic semiconductor material described in the first aspect in the fabrication of optoelectronic devices.

[0025] Preferably, the optoelectronic device is selected from one of the following: a circularly polarized light detector, a circularly polarized light-responsive photo-field effect transistor, a circularly polarized organic light-emitting diode, a chiral neuromorphic device, an organic solar cell, and an organic field-effect transistor.

[0026] Compared with the prior art, the intrinsically chiral Y-based organic semiconductor material provided in this application has at least the following beneficial effects: 1. The Y-based organic semiconductor material with intrinsic chirality provided in this application is a Y-based non-fullerene acceptor molecule based on BTP unit. Chiral alkyl side chains are introduced simultaneously at the β-position of thiophene and the N-position of pyrrole in the structure, giving it four chiral sites. This enables high circular dichroism absorption and luminescence characteristics, and the low HOMO energy level is beneficial for achieving efficient charge transport and photogenerated carrier migration. When used as an active layer material for optoelectronic devices, it can make the optoelectronic devices have good chiral asymmetric response, enabling the fabrication of low-power, high-selectivity optoelectronic devices.

[0027] 2. The Y-based organic semiconductor material with intrinsic chirality provided in this application creatively introduces a chiral side chain into the β-thiophene position of the Y-based non-fullerene acceptor molecule during the preparation process; thus providing the possibility of introducing more chiral units into the Y-based non-fullerene acceptor molecule. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0029] Figure 1 The proton NMR spectrum of product 3 prepared by the preparation method provided in Example 1 of this application; Figure 2 The proton NMR spectrum of product 8 prepared by the preparation method provided in Example 1 of this application; Figure 3 The proton NMR spectrum of product 9 prepared by the preparation method provided in Example 2 of this application; Figure 4 The proton nuclear magnetic resonance spectrum of product 10 prepared by the preparation method provided in Example 2 of this application; Figure 5 When the product 10 prepared by the preparation method provided in Example 2 of this application is used as the active layer material of a circularly polarized light detector, the voltage-current density curve of the circularly polarized light detector and the test results of the corresponding asymmetric current parameters are shown. Figure 6 The test diagram of the external quantum efficiency and asymmetric external quantum efficiency parameters of the circularly polarized light detector when the product 10 prepared by the preparation method provided in Example 2 of this application is used as the active layer material of the circularly polarized light detector. Detailed Implementation

[0030] This application provides an intrinsically chiral Y-based organic semiconductor material, its preparation method, and its application, in order to solve the technical problem of the lack of high-performance Y-based organic semiconductor materials in the prior art.

[0031] The technical solutions of this application will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0032] Example 1

[0033] This embodiment provides a method for preparing intrinsically chiral Y-based organic semiconductor materials, the synthetic route of which is shown in Formula A and Formula B; including the oxidation step of chiral alkyl, the nucleophilic addition reaction step, the dehydroxylation step, the cross-coupling reaction step, the nitro reduction reaction step, and the nucleophilic substitution reaction step.

[0034] In the preparation method, the oxidation step of the chiral alkyl group specifically includes: Under a nitrogen atmosphere, (S)-(+)-citronellol (25.00 g, 160 mmol) and Pd / C catalyst (1.28 g, 12 mmol) were mixed in ethyl acetate (250 mL). Hydrogen was introduced into the reaction system via a balloon to carry out the catalytic hydrogenation reaction. The reaction mixture was stirred at room temperature until the balloon volume remained constant, yielding a reaction product solution containing a chiral alkyl alcohol. After the reaction was completed, the reaction product solution was filtered, the filtrate was collected, the solvent was removed, and the product was purified by column chromatography to obtain product 2 (21.00 g, yield 83%).

[0035] At room temperature, product 2 (20.00 g, 126.5 mmol) was slowly added dropwise to a chloroform (100 mL) solution of pyridinium chlorochromate (41.00 g, 190 mmol) and stirred at room temperature for 4 hours to selectively oxidize the primary alcohol, yielding a reaction product solution containing a chiral alkyl aldehyde. After the reaction was completed, the reaction product solution was filtered, the filtrate was collected, the solvent was removed, and the product was purified by column chromatography to obtain product 3 (18.20 g, yield 85%).

[0036] The steps of a nucleophilic addition reaction include: Under a nitrogen atmosphere, a solution of 3-bromothieno[3,2-b]thiophene (3.84 g, 17.5 mmol) in diethyl ether (100 mL) was cooled to -78 °C, and n-butyllithium (7 mL, 17.5 mmol, 2.5 M tetrahydrofuran solution) was added dropwise. The reaction mixture was reacted at -78 °C for 1.5 h to obtain a lithiation solution of 3-bromothieno[3,2-b]thiophene. Product 3 (21.00 mmol, 3.6 g) was rapidly injected, and the reaction mixture was allowed to rise naturally to room temperature and stirred overnight to carry out a nucleophilic addition reaction of the carbonyl group, yielding a reaction product solution containing the first intermediate. After the reaction was completed, the reaction product solution was poured into water, extracted with dichloromethane, the organic layer was separated, washed with water (40 mL) and brine (40 mL), dried with Na2SO4, and the solvent was removed. Column chromatography was performed using petroleum ether and ethyl acetate as eluents to obtain product 4 (3.35 g, yield 65%).

[0037] The dehydroxylation process includes: Under a nitrogen atmosphere at -4°C, aluminum trichloride (2.00 g, 15 mmol) and lithium aluminum hydride (1.14 g, 30 mmol) were slowly added sequentially to diethyl ether (100 mL), and the reaction mixture was stirred for half an hour. Then, the mixture was slowly raised to room temperature and stirred for another 3 hours at room temperature. The reaction mixture was then cooled to 0°C, and a solution of product 4 (10.00 mmol, 3 g) in diethyl ether (15 mL) was added dropwise to the above system. The mixture was allowed to react overnight at room temperature to undergo a dehydroxylation reaction, yielding a reaction product solution containing the second intermediate. After the reaction was completed, the reaction product solution was poured into water, and concentrated hydrochloric acid (10 mL) was slowly added dropwise. The mixture was extracted with dichloromethane, the organic layer was separated, washed with water (40 mL) and brine (40 mL), dried with Na2SO4, and the solvent was removed. The product 5 (2.57 g, 91.7% yield) was obtained by column chromatography using n-hexane as the eluent.

[0038] The steps of a cross-coupling reaction include: Under a nitrogen atmosphere, a tetrahydrofuran (100 mL) solution of product 5 (2.40 g, 8.71 mmol) was cooled to -78°C, and diisopropylaminolithium (3.48 mL, 8.71 mmol, 2.5 M tetrahydrofuran solution) was added dropwise. The reaction mixture was stirred at -78°C for 1.5 hours, and tri-n-butyltin chloride (4.37 g, 13.44 mmol) was added. The reaction system was slowly heated to room temperature and stirred overnight to modify the α-position of the olefin with organotin. After the organotin modification reaction was completed, water was added to quench the reaction, and the organic layer was extracted with n-hexane and washed with a saturated potassium fluoride solution. The mixture was dried with Na2SO4, and the solvent was removed to obtain crude product 6 (4.79 g), which could be used for subsequent reactions without further purification.

[0039] Under a nitrogen atmosphere, product 6 (4.50 g), 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole (1.29 g, 3.35 mmol), and Pd(PPh3)2Cl2 (118 mg, 0.17 mmol) were dissolved in toluene (50 mL). The reaction mixture was heated under reflux and stirred overnight to carry out a Stille cross-coupling reaction, yielding a reaction product solution containing a third intermediate. After the reaction was completed, the product was extracted with dichloromethane, the organic layer was separated, washed with water (40 mL) and brine (40 mL), dried with Na2SO4, and then the solvent was removed. The product was separated by column chromatography using petroleum ether and dichloromethane as eluents to obtain product 7 (2.32 g, yield 87%).

[0040] The steps involved in nitro reduction and nucleophilic substitution reactions include: Under a nitrogen atmosphere, product 7 (1.56 g, 2 mmol) was added to a solution of o-dichlorobenzene (30 mL). Triethyl phosphite (10 mL) was added to the mixture, and the reaction mixture was heated to 180°C and refluxed overnight to reduce the nitro group to an amino group, yielding a reaction product solution containing a nitro-reduced amination product of the third intermediate. After cooling to room temperature, the solvent was removed to obtain a red solid compound. Under a nitrogen atmosphere, the red solid compound, (S)-1-bromo-3,7-dimethyloctane (6.60 g, 32 mmol), potassium carbonate (4.42 g, 32 mmol), and potassium iodide (5.32 g, 32 mmol) were reacted. 32 mmol) was dissolved in N,N-dimethylformamide (50 mL), and the reaction mixture was heated at 80°C overnight to carry out an SN2 nucleophilic substitution reaction of the amino group, giving a reaction product solution containing an intrinsically chiral Y-series organic semiconductor material; the solution was quenched with water, extracted with dichloromethane, the organic layer was separated, washed with water (40 mL) and brine (40 mL), dried with Na2SO4, and then the solvent was removed. The product was separated by column chromatography using petroleum ether and dichloromethane as eluents, yielding product 8 (1.14 g, yield 59%), which is (S)-3,7-dimethyloctyl modified dithiophene-thiophene-pyrrolobenzothiadiazole (BTP), in which chiral alkyl side chains are introduced at both the β-position of the thiophene and the N-position of the pyrrole.

[0041] Formula A; Formula B.

[0042] Example 2

[0043] This embodiment provides a method for preparing intrinsically chiral Y-based organic semiconductor materials, the synthetic route of which is shown in Formula C; including a formylation reaction step and a Knoevenagel condensation reaction step.

[0044] In the preparation method, the formylation reaction step includes: Under a nitrogen atmosphere, a tetrahydrofuran (50 mL) solution of product 8 (0.97 g, 1 mmol) was cooled to -78 °C, and n-butyllithium (1 mL, 2.5 mmol, 2.5 M tetrahydrofuran solution) was added dropwise. The reaction mixture was reacted at -78 °C for 1.5 hours, and then N,N-dimethylformamide (5 mL) was added. The reaction system was slowly heated to room temperature and stirred overnight to carry out the formylation reaction, yielding a reaction product solution containing product 9. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, and the organic layer was separated. The organic layer was washed with water (40 mL) and brine (40 mL), dried with Na2SO4, and then the solvent was removed. The product 9 was obtained by column chromatography using petroleum ether and dichloromethane as eluents.

[0045] The steps of the Knoevenagel condensation reaction include: Under a nitrogen atmosphere, product 9 (0.50 g, 0.5 mmol) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (0.53 mg, 2.5 mmol) were dissolved in chloroform (100 mL) and stirred for 30 minutes. Pyridine (2.5 mL) was added dropwise to the reaction system, and the mixture was heated to 55°C and reacted for 6 hours to carry out the Knoevenagel condensation reaction, yielding a reaction product solution containing product 10. After cooling to room temperature, the solvent was removed, and the product was separated by column chromatography using petroleum ether and dichloromethane as eluents to obtain product 10 (0.63 g, yield 88%), which is a Y-series non-fullerene acceptor molecule ((S,S,S,S)-BTP-4F) based on the BTP unit.

[0046] Formula C.

[0047] Experimental Example 1

[0048] This experimental example performs structural characterization and performance testing on products 3, 8, 9, and 10 prepared in Examples 1-2, and the results are as follows: Figures 1-6 As shown.

[0049] The proton NMR spectra of products 3, 8, 9, and 10 in the structural characterization are shown below. Figures 1-4 As shown, it can be seen that the preparation methods provided in Examples 1-2 of this application can successfully prepare products 3, 8, 9 and 10.

[0050] The performance test was conducted as follows: Product 10 provided in Example 2, namely the Y-based non-fullerene acceptor molecule (S,S,S,S)-BTP-4F based on the BTP unit, was used as the active layer material of a circularly polarized light detector. Its preparation process included: first, cleaning an indium tin oxide (ITO) glass substrate with deionized water, acetone, and isopropanol, followed by purging with nitrogen; then, spin-coating a poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) aqueous solution onto the ITO substrate at 2500 rpm, followed by thermal annealing at 150 °C for 10 minutes; subsequently, chiral non-fullerene acceptor molecules were added at a concentration of 10 mg / mL... -1 The concentration was dissolved in chloroform and spin-coated onto PEDOT:PSS at a speed of 2500 rpm. A methanol solution of F3NBr was spin-coated as an interface modification, and a 120 nm silver electrode was deposited on the active layer to complete the fabrication of the circularly polarized light detector. Voltage-current density curves and corresponding asymmetric current parameters (g) were obtained by applying different voltages to the fabricated circularly polarized light detector. current )like Figure 5 As shown, the external quantum efficiency and asymmetric external quantum efficiency parameters (g) at different wavelengths are...sc )like Figure 6 As shown; from Figure 5 and Figure 6 As can be seen, since the circularly polarized light detector uses the Y-based non-fullerene acceptor molecule (S,S,S,S)-BTP-4F based on the BTP unit provided in Example 2 as the active layer material of the circularly polarized light detector, (S,S,S,S)-BTP-4F introduces chiral alkyl side chains at the β-position of thiophene and the N-position of pyrrole, achieving high circular dichroism absorption and emission characteristics. Moreover, based on the Y-based non-fullerene acceptor, the highest occupied molecular orbital HOMO energy level is low, which is conducive to achieving efficient charge transport and photogenerated carrier migration. This makes the circularly polarized light detector have good chiral asymmetric response, making it suitable as a low-power, high-selectivity chiral polarized light detector.

[0051] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A Y-based organic semiconductor material with intrinsic chirality, characterized in that, The general chemical formula is shown in Formula I; Equation I; In Formula I, R is a chiral alkyl side chain, and R1 is selected from at least one of hydrogen-based, aldehyde-based, and (2,3-dicyano-4-aryl-3-oxo-2,3-dihydro-1H-indene-1-yl) vinyl groups.

2. The intrinsically chiral Y-based organic semiconductor material according to claim 1, characterized in that, R1 is selected from hydrogen-based materials, and the chemical structure of the intrinsically chiral Y-based organic semiconductor material is shown in Formula II. Formula II; In Formula II, R is selected from one of the following chiral alkyl side chains: 。 3. The intrinsically chiral Y-based organic semiconductor material according to claim 1, characterized in that, R1 is selected from aldehyde groups, and the chemical structure of the intrinsically chiral Y-based organic semiconductor material is shown in Formula III. Formula III; In Formula III, R is selected from one of the following chiral alkyl side chains: 。 4. The intrinsically chiral Y-based organic semiconductor material according to claim 1, characterized in that, R1 is selected from (2,3-dicyano-4-aryl-3-oxo-2,3-dihydro-1H-inden-1-yl) vinyl, and the chemical structure of the intrinsically chiral Y-based organic semiconductor material is shown in Formula IV; Formula IV; In Formula IV, R is selected from one of the following chiral alkyl side chains: ； In R1, Ar is selected from one of the following aryl groups: 。 5. A method for preparing an intrinsically chiral Y-based organic semiconductor material, characterized in that, The preparation of an intrinsically chiral Y-based organic semiconductor material according to any one of claims 1-4 includes the following steps: Selective oxidation of primary alcohols in chiral alkyl alcohols yields chiral alkyl aldehydes; A nucleophilic addition reaction of carbonyl groups was carried out on a lithiumized solution containing chiral alkyl aldehydes and 3-bromothiophene[3,2-b]thiophene to give the first intermediate product; The first intermediate was subjected to a dehydroxylation reaction using a dehydroxylation reagent to obtain the second intermediate. After modifying the α-position of the olefin of the second intermediate with organotin, it was reacted with 4,7-dibromo-5,6-dinitrobenzothiadiazole via a Stille cross-coupling reaction to obtain the third intermediate. The nitro group in the third intermediate is reduced to an amino group to obtain the nitro-reduced amination product of the third intermediate. The nitro-reduced amination product of the third intermediate and the chiral alkyl bromide were subjected to an SN2 nucleophilic substitution reaction of the amino group to obtain an intrinsically chiral Y-series organic semiconductor material.

6. The method for preparing an intrinsically chiral Y-based organic semiconductor material according to claim 5, characterized in that, Following the SN2 nucleophilic substitution reaction of the amino group, the reaction further includes: sequential formylation with a lithium-ionized solution and N,N-dimethylformamide; and reactions with 2-(3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, 2-(5-chloro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile, and 2-(4,5,6,7-tetrachloro-3-oxo-2,3-dihydro-1H-indene-1-yl)malonitrile. The following malononitrile, 2-(5-bromo-3-oxo-2,3-dihydro-1H-indene-1-ylidene) malononitrile, 2-(5,6-difluoro-1-naphthyl-3-oxo-2,3-dihydro-1H-indene-1-ylidene) malononitrile, 2-(5-methyl-3-oxo-2,3-dihydro-1H-indene-1-ylidene) malononitrile, 2-(4-oxo-4,5-dihydro-6H-cyclopentathiophene-6-ylidene) malononitrile, and 2-(3-chloro-6-oxo-5,6-dihydro-4H-cyclopentathiophene-4-ylidene) maleidonitrile undergoes a Knoevenagel condensation reaction.

7. The method for preparing an intrinsically chiral Y-based organic semiconductor material according to claim 5, characterized in that, The nucleophilic addition reaction of the carbonyl group includes: cooling a solution of 3-bromothiophene[3,2-b]thiophene to -70~-85℃ under a protective atmosphere, adding n-butyllithium dropwise for 1~3h to obtain a lithiumized solution of 3-bromothiophene[3,2-b]thiophene, adding a chiral alkyl aldehyde, and naturally heating to room temperature and stirring overnight to carry out the nucleophilic addition reaction of the carbonyl group; The SN2 nucleophilic substitution reaction of the amino group is carried out at a temperature of 70-90°C for an overnight reaction.

8. The method for preparing an intrinsically chiral Y-based organic semiconductor material according to claim 6, characterized in that, The formylation reaction process includes: under a protective atmosphere, reacting the product of the SN2 nucleophilic substitution reaction of the amino group with a lithium solution at -70~-85℃ for 1~3h, then adding N,N-dimethylformamide and naturally heating to room temperature and stirring overnight to carry out the formylation reaction; The Knoevenagel condensation reaction was carried out at a temperature of 50-60°C for 4-8 hours under a protective atmosphere.

9. A circularly polarized light detector, characterized in that, Its active layer material includes a Y-based organic semiconductor material with intrinsic chirality as described in any one of claims 1-4.

10. The application of an intrinsically chiral Y-based organic semiconductor material according to any one of claims 1-4 in the fabrication of optoelectronic devices.

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