Chiral macromolecular electron acceptor material and application thereof

Abstract

The invention discloses a chiral macromolecular electron acceptor material and application thereof, and relates to the technical field of chiral photoelectric materials and photoelectric detection. A non-fullerene electron acceptor material with near-infrared absorption capability is linked by a chiral pure linking group to form a structural general formula shown in the specification: # imgabs0 #, in the formula, n is greater than or equal to 1, NFA is a non-fullerene electron acceptor material, and C is a chiral pure linking unit. Wherein the non-fullerene electron acceptor material is selected from any one of the following structures: # imgabs 1 #. The chiral pure macromolecular electron acceptor material provided by the invention is simple and convenient to synthesize, the structure is easy to regulate and control, good response is realized in a near-infrared region, and direct detection of near-infrared circularly polarized light is realized; high external quantum efficiency, responsivity, detectivity, response speed and photocurrent asymmetry factor (gsc) are obtained, and good commercial application prospects are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of chiral photoelectric materials and photoelectric detection, and in particular to a chiral macromolecular electron acceptor material and application thereof. Background Art

[0002] In optical technology, circularly polarized light and linearly polarized light are two important polarization states, each with its own characteristics in terms of generation method, visual experience, and technical application. Circularly polarized light (CPL) is a special elliptically polarized light that can be generated by two linearly polarized lights (LPL) with perpendicular electric field vectors. The electric field vector of linearly polarized light is limited to one direction, such as the vertical direction, and the vector is the result of having both x and y vibrating electric field vector components. The electric field vector of CPL can be decomposed into two orthogonal LPL electric field vectors, with a 90° phase shift between the two electric field vectors. When the phase difference is ±90°, the synthesized electric field vector forms a circle, and the polarized light at this time is CPL. From the direction of the sensor, if the electric field vector of CPL rotates in the counterclockwise direction, the CPL at this time is called RCP light. On the contrary, if the electric field vector of CPL rotates in the clockwise direction, the CPL at this time is called LCP light.

[0003] LPL technology is widely used in polarized sunglasses, liquid crystal displays and other fields, especially in reducing reflected light and glare. CPL detection technology has shown unique applications in drug screening, quantum communication, biomedical imaging and other fields, and has become one of the most emerging technologies. Its specific practical application is closely related to the working wavelength. Traditional CPL detection usually uses optical components, including linear polarizers and quarter-wave plates, and their stacked structure complicates the development of integrated circuits. Chiral organic semiconductor materials, chiral organic-inorganic hybrid perovskite materials and superchiral materials are new materials developed in recent years for direct CPL detection. In particular, chiral organic semiconductor materials have been proven to be a promising class of optoelectronic materials suitable for CPL-sensitive related research.

[0004] Chiral organic semiconductor materials have the characteristics of variable structure, tunable spectrum, small dark current and high detection ratio. Organic photodetectors based on chiral organic semiconductor materials have the advantage of low noise and can sensitively convert the polarization characteristics of near-infrared (NIR) circularly polarized light (CPL) into modulated electrical signals; and can prepare flexible, foldable, bendable and stretchable detectors; showing broad application prospects in the fields of spectroscopy, imaging, and communications. Compared with the visible light band, near-infrared light, especially at common wavelengths such as 830, 850, 980, 1060, and 1550nm, has deeper tissue penetration depth, higher resolution and lower light source cost. Therefore, direct CPL detection for these wavelengths is very attractive. However, there are few reports on direct CPL detection of near-infrared light based on chiral organic semiconductor materials. Summary of the invention

[0005] The present invention provides a chiral macromolecular electron acceptor material and its application, aiming to solve the problems existing in the above-mentioned background technology, by linking a non-fullerene electron acceptor material with near-infrared absorption ability with a chirally pure linking group. The photodetector based on these chiral macromolecular electron acceptor materials has the advantages of high photocurrent asymmetry factor, responsivity, detection rate and response speed.

[0006] In order to achieve the above technical objectives, the present invention mainly adopts the following technical solutions:

[0007] In the first aspect, the present invention discloses a chiral macromolecular electron acceptor material, which is formed by linking a non-fullerene electron acceptor material having near-infrared absorption capability with a chirally pure linking group to form the following general structural formula:

[0008]

[0009] Wherein, n≥1, NFA is a non-fullerene electron acceptor material, and C is a chirally pure linking unit.

[0010] In a preferred embodiment of the present invention, the non-fullerene electron acceptor material is selected from any one of the following structures:

[0011]

[0012] Among them, X 1-15 The same or different groups are selected from O, NR, S, Se; the R group in NR is the same as R 1-13 The same or different linear, branched or cyclic alkyl, alkoxy, thioalkyl, ester, silyl or alkyl, alkoxy, thioalkyl, ester, silyl substituted aromatic rings having 1 to 30 carbon atoms, the aromatic rings including benzene, thiophene, furan and selenophene; m and n are integers ranging from 0 to 4; EG3-8 It is an electron withdrawing group containing cyanoindanone or indanone.

[0013] Preferably, the electron withdrawing group containing cyanoindanone or indanone is selected from any one of the following groups:

[0014]

[0015] Among them, X 1-4 independently selected from F, Cl, Br, I atoms, or alkyl, alkoxy, thioalkyl having 1-3 carbon atoms or their corresponding fully fluorinated or partially fluorinated derivatives; Y is selected from O, S, Se atoms'.

[0016] In a preferred embodiment of the present invention, the chirally pure linking unit is selected from any one of the following structural formulas:

[0017]

[0018] Preferably, compound R-3, compound S-3, compound R-6, compound S-6, compound R-9, compound S-9, compound M, M-12, compound P, P-12, compound M, M-15, compound P, P-15, compound PR-17, compound PS-19, compound P (P, P-21), compound P-25, compound PS-28, compound PS-31, compound PS-35;

[0019]

[0020]

[0021]

[0022]

[0023] In a second aspect, the present invention further discloses an application of the chiral macromolecular electron acceptor material as described in the first aspect in the preparation of an organic photodetector, wherein the organic photodetector is a near-infrared circularly polarized light detector, and the near-infrared circularly polarized light detector includes a bulk heterojunction device and a layer-by-layer processing device.

[0024] In a third aspect, the present invention further discloses a bulk heterojunction device, characterized in that it comprises the chiral macromolecular electron acceptor material and donor material described in the first aspect, and the mass ratio of the electron acceptor material to the donor material is 1:1-25.

[0025] In a fourth aspect, the present invention further discloses a method for preparing a bulk heterojunction device as described in the third aspect, comprising first dissolving an electron acceptor material and a donor material in an organic solvent and mixing them evenly, spin coating them on an annealed substrate to obtain an active layer, and then performing conventional treatment to prepare a bulk heterojunction device.

[0026] In a fifth aspect, the present invention further discloses a layer-by-layer processing device, comprising the chiral macromolecular electron acceptor material and donor material described in the first aspect, wherein the concentration of the electron acceptor material and the donor material is 2-30 mg mL -1 .

[0027] In the sixth aspect, the present invention also discloses a method for preparing a layer-by-layer processing device as described in the fifth aspect, comprising dissolving an electron acceptor material and a donor material in an organic solvent to prepare an acceptor solution and a donor solution, respectively, and then spin-coating the donor solution on an annealed substrate, and then spin-coating the acceptor solution on top of the donor layer to obtain an active layer, and then performing conventional treatment to prepare a layer-by-layer processing device.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The chiral-pure macromolecular electron acceptor material provided by the present invention is easy to synthesize, has an easily controllable structure, has a good response in the near-infrared region, realizes direct detection of near-infrared circularly polarized light, obtains high external quantum efficiency, responsivity, detection rate and response speed, and the photocurrent asymmetry factor (g sc ), has good commercial application prospects. DETAILED DESCRIPTION

[0030] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with embodiments.

[0031] Example 1

[0032] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0033]

[0034] Compound 1 (1 eq) and compound R-2 (0.5 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (2eq), acetic anhydride (5eq) and toluene in appropriate amounts, react at 60°C until no raw material can be detected by thin layer chromatography (TCL). The product is washed with water and extracted three times with dichloromethane. The organic phases are combined, dried over anhydrous sodium sulfate, and then the solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product R-3 with a yield of 95%;

[0035] Elemental analysis of product R-3 (%): C, 73.50; H, 8.02; Cl, ​​1.81; F, 0.97; N, 10.01; O, 5.00; S, 1.64.

[0036] Mass spectrum analysis of product R-3: 3468.33.

[0037] Example 2

[0038] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0039]

[0040] Compound 1 (1 eq) and compound S-2 (0.5 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (2eq), acetic anhydride (5eq) and toluene in appropriate amounts, react at 60°C until no raw material can be detected by thin layer chromatography (TCL). The product is washed with water and extracted three times with dichloromethane. The organic phases are combined, dried over anhydrous sodium sulfate, and then the solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product S-3 with a yield of 95%;

[0041] Elemental analysis of product S-3 (%): C, 73.51; H, 8.01; Cl, ​​1.82; F, 0.97; N, 10.03; O, 5.01; S, 1.65.

[0042] Product S-3 mass spectrum analysis: 3468.33.

[0043] Example 3

[0044] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0045]

[0046] Compound 4 (1 eq) and compound R-5 (0.5 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (2eq), acetic anhydride (5eq) and toluene in appropriate amounts, react at 60°C until no raw material can be detected by thin layer chromatography (TCL). The product is washed with water and extracted three times with dichloromethane. The organic phases are combined, dried over anhydrous sodium sulfate, and the solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product R-6 with a yield of 93%;

[0047] Elemental analysis of product R-6 (%): C, 64.46; H, 5.38; F, 3.11; N, 6.12; O, 2.62; S, 1.75; Se, 17.21.

[0048] Mass spectrum analysis of product R-6: 3702.82.

[0049] Example 4

[0050] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0051]

[0052] Compound 4 (1 eq) and compound S-5 (0.5 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (2eq), acetic anhydride (5eq) and toluene in appropriate amounts, react at 60°C until no raw material can be detected by thin layer chromatography (TCL). The product is washed with water and extracted three times with dichloromethane. The organic phases are combined, dried over anhydrous sodium sulfate, and the solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product S-6 with a yield of 93%;

[0053] Elemental analysis of product S-6 (%): C, 64.45; H, 5.37; F, 3.11; N, 6.11; O, 2.62; S, 1.75; Se, 17.20.

[0054] Mass spectrum analysis of product S-6: 3702.82.

[0055] Example 5

[0056] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0057]

[0058] Compound 7 (1 eq) and compound R-8 (0.5 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (2eq), acetic anhydride (5eq) and toluene in appropriate amounts, react at 60°C until no raw material can be detected by thin layer chromatography (TCL). The product is washed with water and extracted three times with dichloromethane, the organic phases are combined, dried over anhydrous sodium sulfate, and the solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product R-9 with a yield of 90%;

[0059] Elemental analysis of product R-9 (%): C, 71.27; H, 6.55; Cl, ​​4.12; N, 6.51; O, 2.79; S, 9.32.

[0060] Mass spectrum analysis of product R-9: 3458.36.

[0061] Example 6

[0062] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0063]

[0064] Compound 7 (1 eq) and compound S-8 (0.5 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (2eq), acetic anhydride (5eq) and toluene in appropriate amounts, react at 60°C until no raw material can be detected by thin layer chromatography (TCL). The product is washed with water and extracted three times with dichloromethane, the organic phases are combined, dried over anhydrous sodium sulfate, and the solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product S-9 with a yield of 90%;

[0065] Elemental analysis of product S-9 (%): C, 71.28; H, 6.56; Cl, ​​4.13; N, 6.52; O, 2.79; S, 9.33.

[0066] Product S-9 mass spectrum analysis: 3458.36.

[0067] Example 7

[0068] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0069]

[0070] Compound 10 (1 eq), compound M, M-11 (0.5 eq), catalyst Pd(PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3 (6eq), added to the reaction bottle, evacuated nitrogen, then added an appropriate amount of solvent dimethyl sulfoxide (DMSO), reacted at 120°C for 72 hours, until the raw material could not be detected by thin layer chromatography (TCL). The product was washed with water and extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The product was separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product M, M-12 with a yield of 89%;

[0071] Elemental analysis of product M, M-12 (%): C, 72.23; H, 6.81; Cl, ​​3.14; F, 0.84; N, 6.20; O, 4.24; S, 7.10.

[0072] Product M, M-12 mass spectrum analysis: 4546.99.

[0073] Example 8

[0074] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0075]

[0076] Compound 10 (1 eq), compound P, P-11 (0.5 eq), catalyst Pd (PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3 (6eq), added to the reaction bottle, evacuated nitrogen, then added an appropriate amount of solvent dimethyl sulfoxide (DMSO), reacted at 120°C for 72 hours, until the raw material could not be detected by thin layer chromatography (TCL). The product was washed with water and extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The product was separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product P, P-12 with a yield of 89%;

[0077] Elemental analysis of product P, P-12 (%): C, 72.22; H, 6.80; Cl, ​​3.14; F, 0.84; N, 6.19; O, 4.23; S, 7.09.

[0078] Mass spectrometry analysis of product P, P-12: 4546.99.

[0079] Example 9

[0080] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0081]

[0082] Compound 11 (1 eq), compound M, M-12 (0.5 eq), catalyst Pd(PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3(6eq), added to the reaction bottle, evacuated nitrogen, then added an appropriate amount of solvent dimethyl sulfoxide (DMSO), reacted at 120°C for 72 hours, until the raw material could not be detected by thin layer chromatography (TCL). The product was washed with water and extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The product was separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product M, M-15 with a yield of 89%;

[0083] Elemental analysis of product M, M-15 (%): C, 71.80; H, 6.61; Cl, ​​4.54; F, 0.81; N, 5.97; O, 4.09; S, 6.84.

[0084] Product M, M-15 mass spectrum analysis: 4714.94.

[0085] Example 10

[0086] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0087]

[0088] Compound 11 (1 eq), compound P, P-12 (0.5 eq), catalyst Pd(PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3 (6eq), added to the reaction bottle, evacuated nitrogen, then added an appropriate amount of solvent dimethyl sulfoxide (DMSO), reacted at 120°C for 72 hours, until the raw material could not be detected by thin layer chromatography (TCL). The product was washed with water and extracted three times with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The product was separated by silica gel column chromatography using dichloromethane: petroleum ether in a ratio of 2:1 as the eluent to obtain the product P, P-15 with a yield of 89%;

[0089] Elemental analysis of product P, P-15 (%): C, 71.81; H, 6.62; Cl, ​​4.54; F, 0.81; N, 5.98; O, 4.10; S, 6.85.

[0090] Mass spectrometry analysis of product P, P-15: 4714.94.

[0091] Embodiment 11

[0092] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0093]

[0094] Compound 16 (1 eq), compound R-1 (1 eq), catalyst Pd(PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3 (6eq), add to the reaction bottle, exhaust nitrogen, then add an appropriate amount of solvent dimethyl sulfoxide (DMSO), react at 120°C, and add compound 16 (1.1eq) after 72h of reaction. After 24h of reaction, cool to room temperature, slowly pour the reaction system into 100mL of methanol and collect the solid by suction filtration. Then extract with methanol, n-hexane, acetone, dichloromethane, chloroform and chlorobenzene in turn, collect the dichloromethane phase, chloroform phase and chlorobenzene phase fractions respectively and concentrate, then precipitate with methanol, and dry under vacuum to obtain the solid product PR-17 with a yield of 86%;

[0095] Elemental analysis (%) of product PR-17: C, 70.61; H, 6.55; Br, 2.31; F, 2.21; N, 6.51; O, 2.77; S, 9.30.

[0096] Example 12

[0097] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0098]

[0099] Compound 18 (1 eq) and compound S-8 (1 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (4eq), acetic anhydride (10eq) and toluene in appropriate amounts, react at 60°C for 24h, then add IC-2Cl (1eq); continue to react for 24h, add compound 7 (1eq), react for 24h, cool to room temperature, slowly pour the reaction system into 100mL methanol and collect the solid by suction filtration. Then extract with methanol, n-hexane, acetone, dichloromethane, chloroform and chlorobenzene in turn, collect the dichloromethane phase, chloroform phase and chlorobenzene phase fractions respectively and concentrate, then precipitate with methanol, and dry under vacuum to obtain the solid product PS-20 with a yield of 86%.

[0100] Elemental analysis of product PS-19 (%): C, 70.88; H, 6.50; Cl, ​​4.11; N, 6.51; O, 2.82; S, 9.33.

[0101] Example 13

[0102] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0103]

[0104] Compound 20 (1 eq), compound P, P-14 (1 eq), catalyst Pd (PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3 (6eq), added to the reaction bottle, evacuated nitrogen, then added an appropriate amount of solvent dimethyl sulfoxide (DMSO), reacted at 120°C, reacted for 72h, added compound 20 (1.1eq), and then continued to react for 24h, cooled to room temperature, slowly poured the reaction system into 100mL methanol and filtered to collect the solid. Then extracted with methanol, n-hexane, acetone, dichloromethane, chloroform and chlorobenzene in turn, collected the dichloromethane phase, chloroform phase and chlorobenzene phase fractions and concentrated them, then precipitated with methanol, and dried under vacuum to obtain the solid product P (P, P-21), with a yield of 81%;

[0105] Elemental analysis (%) of product P (P, P-21): C, 72.30; H, 6.89; Br, 1.79; F, 1.67; O, 4.26; S, 7.09.

[0106] Embodiment 14

[0107] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0108]

[0109] Compound 22 (1 eq) and compound 23 (1 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (4eq), acetic anhydride (10eq) and toluene in appropriate amounts, react at 60°C for 24h, add IC-24 (2.2eq), then continue to react for 24h, add compound 7 (1eq), react for 24h; cool to room temperature, slowly pour the reaction system into 100mL methanol and collect the solid by suction filtration. Then extract with methanol, n-hexane, acetone, dichloromethane, chloroform and chlorobenzene in turn, collect the dichloromethane phase, chloroform phase and chlorobenzene phase fractions respectively and concentrate, then precipitate with methanol, and dry under vacuum to obtain the solid product P-25 with a yield of 70%.

[0110] Elemental analysis of product P-25 (%): C, 58.51; H, 3.35; Br, 2.45; Cl, ​​7.63; F, 1.75; N, 6.88; O, 5.90; S, 3.93; Se, 9.70.

[0111] Embodiment 15

[0112] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0113]

[0114] Compound 26 (1 eq), compound S-27 (1 eq), catalyst Pd(PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3 (6eq), add to the reaction bottle, exhaust nitrogen, then add an appropriate amount of solvent dimethyl sulfoxide (DMSO), react at 120°C, and add compound 26 (1.1eq) after 72 hours of reaction. After 24 hours of reaction, cool to room temperature, slowly pour the reaction system into 100mL of methanol and collect the solid by suction filtration. Then extract with methanol, n-hexane, acetone, dichloromethane, chloroform and chlorobenzene in turn, collect the dichloromethane phase, chloroform phase and chlorobenzene phase fractions respectively and concentrate, then precipitate with methanol, and dry under vacuum to obtain the solid product PS-28 with a yield of 80%;

[0115] Elemental analysis of product PS-28 (%): C, 72.78; H, 7.23; Br, 3.14; N, 5.08; O, 4.14; S, 6.64.

[0116] Example 16

[0117] A chirally pure macromolecular electron acceptor material, the preparation method of which is as follows:

[0118]

[0119] Compound 29 (1 eq), compound S-30 (1 eq), catalyst Pd(PPh 3 ) 2 Cl 2 (0.03eq), K 2 CO 3 (6eq), add to the reaction bottle, exhaust nitrogen, then add an appropriate amount of solvent dimethyl sulfoxide (DMSO), react at 120°C for 72 hours; add compound 29 (0.3eq). After reacting for 24 hours, cool to room temperature, slowly pour the reaction system into 100mL of methanol and collect the solid by filtration. Then extract with methanol, n-hexane, acetone, dichloromethane and chloroform in turn, collect the dichloromethane phase fraction and concentrate, then precipitate with methanol, and dry under vacuum to obtain the solid product PS-31 with a yield of 83%;

[0120] Elemental analysis of product PS-31 (%): C, 62.05; H, 5.20; Br, 2.54; Cl, ​​4.50; N, 3.56; O, 4.05; S, 8.15; Se, 10.02.

[0121] Embodiment 17

[0122] A chirally pure macromolecular electron acceptor, the preparation method of which is as follows:

[0123]

[0124] Compound 32 (1 eq) and compound S-33 (1 eq) were added to the reaction flask, nitrogen was evacuated, and BF 3 ·OEt 2 (4eq), acetic anhydride (10eq) and toluene in appropriate amounts, react at 60°C for 24h, add IC-34 (0.3eq), react for 24h; add compound 7 (0.3eq), react for 24h, cool to room temperature, slowly pour the reaction system into 100mL methanol and collect the solid by suction filtration. Then extract with methanol, n-hexane, acetone, dichloromethane, chloroform and chlorobenzene in turn, collect the dichloromethane phase, chloroform phase and chlorobenzene phase fractions respectively and concentrate, then precipitate with methanol, and dry under vacuum to obtain the solid product PS-35 with a yield of 72%.

[0125] Elemental analysis of product PS-35 (%): C, 76.25; H, 6.26; Cl, ​​2.07; F, 1.67; N, 4.10; O, 5.13; Se, 4.61.

[0126] Test example

[0127] An organic photodetector was prepared using the compound R-3 prepared in Example 1, the compound S-3 prepared in Example 2, the compound R-6 prepared in Example 3, the compound S-6 prepared in Example 4, the compound R-9 prepared in Example 5, the compound S-9 prepared in Example 6, the compounds M, M-12 prepared in Example 7, the compounds P, P-12 prepared in Example 8, the compounds M, M-15 prepared in Example 9, the compounds P, P-15 prepared in Example 10, the compound PR-17 prepared in Example 11, the compound PS-19 prepared in Example 12, the compound P(P, P-21) prepared in Example 13, the compound P-25 prepared in Example 14, the compound PS-28 prepared in Example 15, the compound PS-31 prepared in Example 16 and the compound PS-35 prepared in Example 17 as electron acceptor materials. The specific preparation method is as follows: a glass substrate covered with indium tin oxide (ITO) was cleaned with detergent, ultrapure water, acetone, and isopropanol in sequence, and each step was ultrasonically treated for 20 minutes. Then, a zinc oxide (ZnO) layer was spin-coated onto the ITO substrate at 4000 rpm. Then, 0.1 vol% 2-phenylethyl sulfide (PET) was dissolved in methanol and spin-coated at 3000 rpm to remove the hydroxyl groups on the surface of zinc oxide to improve the stability of the device, and then thermally annealed at 120°C for 10 min in a nitrogen-filled glove box.

[0128] For bulk heterojunction (BHJ) devices, 17 electron acceptor materials and donor material PM6 were dissolved in organic solvents at a mass ratio of 1:10 to prepare solutions (as shown in Table 1, with a total solution concentration of 16 or 18 mg mL -1 ) was spin-coated on the annealed substrate for 40 seconds to form a film with a thickness of about 100 nm, with a rotation speed ranging from 4000 to 1000 rpm. The active layer was then thermally annealed at 120°C for 10 minutes. Subsequently, PET was dissolved in methanol and coated on the active layer at 3000 rpm for 30 seconds. Finally, the vacuum was set at 1×10 -5 MoO was prepared by thermal evaporation under Pa conditions. x and Al electrodes to obtain an organic photodetector device. Finally, under L-CPL and R-CPL illumination at a wavelength of 830nm, the light intensity was 0.03mW·cm -2 The basic performance of the CPL detector was tested under the following conditions, and the average results are shown in Table 1.

[0129] Table 1 Main light detection performance parameters of BHJ CPL detectors based on 17 receptor materials

[0130]

[0131]

[0132] Among them, CF: chloroform; CN: chloronaphthalene; Tol: toluene.

[0133] For the layer-by-layer (LBL) device, the donor and 17 acceptor materials were dissolved in organic solvents to prepare solutions (as shown in Table 2, the solution concentration was 8 mg mL -1 ), the donor solution was first spin-coated on the substrate at 2300 rpm for 40 s. Then the acceptor solution was spin-coated on top of the donor layer at 2000 rpm for 40 s. The active layer was then thermally annealed at 120 °C for 10 min. Subsequently, PET was dissolved in methanol and coated on the active layer at 3000 rpm for 30 s. Finally, the vacuum was set to 1×10 -5 MoO was prepared by thermal evaporation under Pa conditions. x and Al electrodes to obtain organic photodetector devices. Ten devices of each of the 17 electron acceptor materials in the above examples were prepared. Finally, under L-CPL and R-CPL illumination at a wavelength of 830 nm, the light intensity was 0.03 mW·cm -2 The basic performance of the CPL detector was tested under the following conditions, and the average results are shown in Table 2.

[0134] Table 2 Main light detection performance parameters of LBL CPL detectors based on 17 electron acceptors

[0135]

[0136]

[0137] Among them, CF: chloroform; CN: chloronaphthalene; Tol: toluene.

[0138] R represents responsivity, D* represents specific detectivity, EQE represents external quantum efficiency, g sc represents the photocurrent asymmetry factor.

[0139] It can be seen from Tables 1 and 2 that the various light detection performance parameters of chirally pure macromolecular electron acceptor materials are relatively high, indicating that they have great potential for application in acceptor materials for organic photodetectors.

[0140] It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A chiral macromolecular electron acceptor material, characterized in that: By linking a non-fullerene electron acceptor material with near-infrared absorption ability with a chirally pure linking group, a general structural formula is formed as shown below: Wherein, n≥1, NFA is a non-fullerene electron acceptor material, and C is a chirally pure linking unit.

2. The chiral macromolecular electron acceptor material according to claim 1, characterized in that: The non-fullerene electron acceptor material is selected from any one of the following structures: Among them, X 1-15 The same or different groups are selected from O, NR, S, Se; the R group in NR is the same as R 1-13 The same or different linear, branched or cyclic alkyl, alkoxy, thioalkyl, ester, silyl or alkyl, alkoxy, thioalkyl, ester, silyl substituted aromatic rings having 1 to 30 carbon atoms, the aromatic rings including benzene, thiophene, furan and selenophene; m and n are integers ranging from 0 to 4; EG 3-8 It is an electron withdrawing group containing cyanoindanone or indanone.

3. The chiral macromolecular electron acceptor material according to claim 2, characterized in that: The electron withdrawing group containing cyanoindanone or indanone is selected from any one of the following groups: Among them, X 1-4 independently selected from F, Cl, Br, I atoms, or alkyl, alkoxy, thioalkyl, or their corresponding perfluorinated or partially fluorinated derivatives having 1-3 carbon atoms; Y is selected from O, S, Se atoms.

4. The chiral macromolecular electron acceptor material according to claim 1, characterized in that: The chirally pure linking unit is selected from any one of the following structural formulas:

5. The chiral macromolecular electron acceptor material according to any one of claims 1 to 4, characterized in that: Compound R-3, compound S-3, compound R-6, compound S-6, compound R-9, compound S-9, compound M, M-12, compound P, P-12, compound M, M-15, compound P, P-15, compound PR-17, compound PS-19, compound P (P, P-21), compound P-25, compound PS-28, compound PS-31, compound PS-35; 6. Use of the chiral macromolecular electron acceptor material according to claim 1 in the preparation of an organic photodetector, wherein the organic photodetector is a near-infrared circularly polarized light detector, and the near-infrared circularly polarized light detector comprises a bulk heterojunction device and a layer-by-layer processing device.

7. A bulk heterojunction device, characterized in that: The invention comprises the chiral macromolecular electron acceptor material and the donor material according to any one of claims 1 to 5, wherein the mass ratio of the electron acceptor material to the donor material is 1:1-50.

8. The method for preparing a bulk heterojunction device according to claim 7, characterized in that: The method comprises dissolving an electron acceptor material and a donor material in an organic solvent and mixing them uniformly, then spin coating them on an annealed substrate to obtain an active layer, and then performing conventional treatment to prepare a bulk heterojunction device.

9. A layer-by-layer processing device, characterized in that: The invention comprises the chiral macromolecular electron acceptor material and the donor material according to any one of claims 1 to 5, wherein the concentration of the electron acceptor material and the donor material is 2-30 mg mL -1 .

10. The method for preparing a layer-by-layer processing device according to claim 9, characterized in that: The method comprises dissolving the electron acceptor material and the donor material in an organic solvent to prepare an acceptor solution and a donor solution respectively, then spin-coating the donor solution on an annealed substrate, and then spin-coating the acceptor solution on top of the donor layer to obtain an active layer, and then performing conventional treatment to prepare a layer-by-layer processed device.

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