Asymmetric short-wave infrared receptor micromolecule based on quinonoid core unit as well as preparation method and application of asymmetric short-wave infrared receptor micromolecule

Abstract

The invention relates to the field of organic photoelectricity, in particular to an asymmetric short-wave infrared receptor micromolecule based on a quinonoid core unit and a preparation method and application thereof. The structural formula of the asymmetric short-wave infrared receptor micromolecule based on the quinonoid core unit is shown in the specification, B is the quinonoid core unit; pi 1 and pi 2 are bridging units; a is an electron withdrawing unit. The asymmetric short-wave infrared receptor micromolecule based on the quinonoid core unit is applied to preparation of an optical detector or a solar cell as an optical detection material or a photovoltaic material, and the optical detector prepared from the material has a relatively high specific detection rate in a short-wave infrared region. The preparation method provided by the invention has the advantages of being simple in process, high in yield, flexible in structure adjustment, low in manufacturing cost, suitable for industrial production and the like.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronics, and in particular to an asymmetric short-wave infrared receptor small molecule based on a quinone core unit, its preparation method, and its application. Background Technology

[0002] The emergence of non-fullerene acceptors has driven the rapid development of organic photovoltaics, gradually increasing the energy conversion efficiency of organic solar cells to over 20%, and also demonstrating great potential for manufacturing highly sensitive organic photodetectors. Organic semiconductor materials, compared to inorganic semiconductor materials, have advantages such as higher absorption coefficients, tunable absorption spectral ranges, light weight, flexibility, and the ability to be processed in large-area solutions.

[0003] For bulk heterojunction organic photodetectors, the specific detectivity (D) * The external quantum efficiency (EQE) and dark current density (J / L) are core parameters for judging the performance of a device. They are primarily influenced by the device's external quantum efficiency (EQE) and dark current density (J / L). d The higher the EQE, the better. d The smaller D is * The larger the wavelength, the better the detection performance of the photodetector. However, due to limitations in the quantity, variety, and properties of organic semiconductor materials, coupled with the constraints of the bandgap law, the recombination of organic materials increases with increasing detection wavelength, leading to variations in the EQE and J of organic photodetectors. d Both will be severely affected. Therefore, it is urgent to design and synthesize a class of organic semiconductor materials that have both long detection wavelengths and good photoelectric properties to improve the detection performance of OPD devices. Summary of the Invention

[0004] Based on the above, this invention provides an asymmetric short-wave infrared acceptor material based on a quinone core unit, which is a short-wave infrared modular non-fullerene acceptor small molecule with an A-π1-Q-π2-A structure. Photodetectors prepared from this small molecule exhibit low dark current and high specific detectivity in the short-wave infrared region.

[0005] To achieve the above objectives, the present invention provides the following solution: One of the technical solutions of this invention is an asymmetric short-wave infrared receptor small molecule based on a quinone core unit, with the following structural formula: ; Wherein, B is a quinone core unit; π1 and π2 are bridging elements; A is an electron-withdrawing unit.

[0006] In a preferred embodiment of the present invention, the quinone core unit is selected from one of the following structural formulas: ; Wherein, Y is any one of oxygen, sulfur, and selenium; R1, R2, and R3 are each any one of the following: substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted ester group, all of which are C1-C30 substituted or unsubstituted.

[0007] In a preferred embodiment of the present invention, the bridging unit is selected from one of the following structural formulas: ; Wherein, X is any one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, and trifluoromethyl; Y can be any one of oxygen, sulfur, and selenium; Z can be any one of carbon, silicon, and germanium; R4-R9 are any one of the following: C1-C16 substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted ester.

[0008] In a preferred embodiment of the present invention, the electron-withdrawing unit is selected from one of the following structural formulas: ; Among them, X1, X2, X3, X4, X5, and X6 are independently any one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, C1-C8 substituted or unsubstituted alkyl, C1-C8 substituted or unsubstituted alkoxy, C1-C8 substituted or unsubstituted alkylthio, C1-C8 substituted or unsubstituted silyl, C1-C8 substituted or unsubstituted aryl, C1-C8 substituted or unsubstituted heteroaryl, and C1-C8 substituted or unsubstituted ester.

[0009] The second technical solution of the present invention is a method for preparing the above-mentioned asymmetric short-wave infrared receptor small molecule based on a quinone core unit, comprising the following steps: Step 1: The monomers of the quinone core unit are reacted with the monomers of the bridging unit in the presence of a catalyst to obtain intermediates; Step 2: React the intermediate with the monomer of the electron-withdrawing unit to obtain the asymmetric short-wave infrared receptor small molecule based on the quinone core unit.

[0010] In a preferred embodiment of the present invention, the molar ratio of the monomer of the quinone core unit to the monomer of each bridging unit is 1:1 to 1:1.5.

[0011] In a preferred embodiment of the invention, the catalyst is selected from palladium-based catalysts.

[0012] The third technical solution of this invention is the application of the aforementioned asymmetric short-wave infrared receptor small molecule based on quinone core units in organic photodetectors.

[0013] The fourth technical solution of the present invention is an organic photodetector, comprising the above-mentioned asymmetric short-wave infrared receptor small molecule based on a quinone core unit.

[0014] In a preferred embodiment of the present invention, a photosensitive layer is included; the photosensitive layer contains asymmetric short-wave infrared receptor small molecules based on quinone core units.

[0015] In a preferred embodiment of the present invention, a hole transport layer and / or an electron transport layer are further included.

[0016] The present invention discloses the following technical effects: 1. This invention provides an asymmetric short-wave infrared acceptor small molecule based on a quinone core unit, which can be used as a photodetector material or photovoltaic material in the preparation of photodetectors or solar cells. The photodetector prepared from this material has low dark current and high specific detectivity in the short-wave infrared region.

[0017] 2. The preparation method provided by the present invention has the advantages of simple process, high yield, flexible structural adjustment, low manufacturing cost and suitability for industrial production. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the organic photodetector structure in the test example.

[0020] Figure 2 Dark current density curves of organic photodetectors fabricated using M1, M2, M3, and M9.

[0021] Figure 3 Dark current density curves of organic photodetectors fabricated using M4, M5, M6, and M10.

[0022] Figure 4 Dark current density curves of organic photodetectors fabricated using M7, M8, and M11.

[0023] Figure 5The external quantum efficiency curves of organic photodetectors fabricated using M1, M2, M3, and M9 are shown.

[0024] Figure 6 External quantum efficiency curves of organic photodetectors fabricated using M4, M5, M6, and M10.

[0025] Figure 7 External quantum efficiency curves of organic photodetectors fabricated using M7, M8, and M11.

[0026] Figure 8 The responsivity curves of the organic photodetectors fabricated using M1, M2, M3, and M9 are shown.

[0027] Figure 9 The responsivity curves of the organic photodetectors fabricated using M4, M5, M6, and M10 are shown.

[0028] Figure 10 The responsivity curves of organic photodetectors fabricated using M7, M8, and M11 are shown.

[0029] Figure 11 The detectivity curves of the organic photodetectors fabricated using M1, M2, M3, and M9 at -0.1V are shown.

[0030] Figure 12 The detectivity curves of the organic photodetectors fabricated using M4, M5, M6, and M10 at -0.1V are shown.

[0031] Figure 13 The detectivity curves of the organic photodetectors fabricated using M7, M8, and M11 at -0.1V are shown. Detailed Implementation

[0032] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0033] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0034] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar to or equivalent to those described herein may be used in the implementation or testing of this invention.

[0035] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0036] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0037] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.

[0038] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0039] The meanings of the English abbreviations used in this invention are as follows: DCE: 1,2-Dichloroethane; DMF: N,N-dimethylformamide; DMSO: Dimethyl sulfoxide.

[0040] Example 1 A small asymmetric short-wave infrared receptor molecule M1 based on a quinone core unit has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 3 Compound 1 (150 mg, 0.24 mmol), compound 2 (177 mg, 0.25 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 1:0) to give compound 3 in 79% yield.

[0041] (2) Synthesis of compound 5 Compound 3 (185 mg, 0.19 mmol), compound 4 (131 mg, 0.19 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to obtain compound 5 in 78% yield.

[0042] (3) Synthesis of compound 6 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 5 (197 mg, 0.15 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) to give compound 6 in 90% yield.

[0043] (4) Synthesis of M1 Compound 6 (182 mg, 0.14 mmol), compound 7 (115 mg, 0.59 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:1) to obtain the target product M1 in 85% yield.

[0044] Example 2 A small asymmetric short-wave infrared receptor molecule, M2, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 3: Same as step (1) in Example 1.

[0045] (2) Synthesis of compound 9 Compound 3 (185 mg, 0.19 mmol), compound 8 (113 mg, 0.19 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to obtain compound 9 in 78% yield.

[0046] (3) Synthesis of compound 10 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 9 (172 mg, 0.15 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) to give compound 10 in 91% yield.

[0047] (4) Synthesis of M2 Compound 10 (167 mg, 0.14 mmol), compound 7 (115 mg, 0.59 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:1) to obtain the target product M2 in 84% yield.

[0048] Example 3 A small asymmetric short-wave infrared receptor molecule, M3, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 3: Same as step (1) in Example 1.

[0049] (2) Synthesis of compound 12 Compound 3 (186 mg, 0.19 mmol), compound 11 (187 mg, 0.19 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to give compound 12 in 75% yield.

[0050] (3) Synthesis of compound 13 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 12 (227 mg, 0.14 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. Compound 13 was obtained by extraction with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 2:5) in 90% yield.

[0051] (4) Synthesis of M3 Compound 13 (201 mg, 0.13 mmol), compound 14 (134 mg, 0.55 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:2) to obtain the target product M3 in 83% yield.

[0052] Example 4 A small asymmetric short-wave infrared receptor molecule, M4, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 15 Compound 1 (150 mg, 0.24 mmol), compound 4 (180 mg, 0.25 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 1:0) to give compound 15 in 70% yield.

[0053] (2) Synthesis of compound 17 Compound 15 (162 mg, 0.17 mmol), compound 16 (125 mg, 0.17 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to give compound 17 in 77% yield.

[0054] (3) Synthesis of compound 18 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 17 (191 mg, 0.15 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) to give compound 18 in 90% yield.

[0055] (4) Synthesis of M4 Compound 18 (181 mg, 0.13 mmol), compound 19 (120 mg, 0.52 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:1) to obtain the target product M4 in 81% yield.

[0056] Example 5 A small asymmetric short-wave infrared receptor molecule, M5, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 15: Same as step (1) in Example 4.

[0057] (2) Synthesis of compound 20 Compound 15 (162 mg, 0.17 mmol), compound 11 (148 mg, 0.17 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to give compound 20 in 76% yield.

[0058] (3) Synthesis of compound 21 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 20 (228 mg, 0.15 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) to give compound 21 in 89% yield.

[0059] (4) Synthesis of M5 Compound 21 (210 mg, 0.13 mmol), compound 22 (119 mg, 0.52 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 2:3) to obtain the target product M5 in 82% yield.

[0060] Example 6 A small asymmetric short-wave infrared receptor molecule, M6, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 24 Compound 23 (146 mg, 0.24 mmol), compound 4 (173 mg, 0.25 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 1:0) to obtain compound 24 in 71% yield.

[0061] (2) Synthesis of compound 25 Compound 24 (159 mg, 0.17 mmol), compound 8 (105 mg, 0.17 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to obtain compound 25 in 74% yield.

[0062] (3) Synthesis of compound 26 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 25 (144 mg, 0.13 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 2:5) to give compound 26 in 91% yield.

[0063] (4) Synthesis of M6 Compound 26 (137 mg, 0.11 mmol), compound 27 (131 mg, 0.5 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:1) to obtain the target product M6 in 80% yield.

[0064] Example 7 A small asymmetric short-wave infrared receptor molecule, M7, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 28 Compound 1 (150 mg, 0.24 mmol), compound 8 (145 mg, 0.25 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 1:0) to give compound 28 in 80% yield.

[0065] (2) Synthesis of compound 29 Compound 28 (147 mg, 0.19 mmol), compound 16 (135 mg, 0.19 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 8:1) to obtain compound 29 in 76% yield.

[0066] (3) Synthesis of compound 30 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 29 (168 mg, 0.14 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) to give compound 30 in 90% yield.

[0067] (4) Synthesis of M7 Compound 30 (160 mg, 0.13 mmol), compound 19 (120 mg, 0.52 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:1) to obtain the target product M7 in 85% yield.

[0068] Example 8 A small asymmetric short-wave infrared receptor molecule, M8, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 32 Compound 31 (160 mg, 0.24 mmol), compound 8 (145 mg, 0.25 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 1:0) to obtain compound 32 in 77% yield.

[0069] (2) Synthesis of compound 34 Compound 32 (166 mg, 0.18 mmol), compound 33 (159 mg, 0.19 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to obtain compound 34 in 75% yield.

[0070] (3) Synthesis of compound 35 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 34 (187 mg, 0.14 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) to give compound 35 in 89% yield.

[0071] (4) Synthesis of M8 Compound 35 (175 mg, 0.12 mmol), compound 36 (106 mg, 0.5 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:1.25) to obtain the target product M8 in 82% yield.

[0072] Comparative Example 1 A symmetric short-wave infrared receptor small molecule, M9, based on a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 37 Compound 1 (150 mg, 0.24 mmol), compound 2 (382 mg, 0.54 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 1:0) to give compound 37 in 56% yield.

[0073] (2) Synthesis of compound 38 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 37 (174 mg, 0.13 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. Compound 38 was obtained by extraction with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) in 90% yield.

[0074] (3) Synthesis of M9 Compound 38 (163 mg, 0.12 mmol), compound 6 (93 mg, 0.48 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:1) to obtain the target product M9 in 83% yield.

[0075] Comparative Example 2 M10, an asymmetric short-wave infrared receptor molecule without a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 40 Compound 39 (120 mg, 0.25 mmol), compound 8 (145 mg, 0.25 mmol), and tetrakis(triphenylphosphine)palladium (14 mg, 0.05 mmol) were added sequentially to a 30 mL pressure-resistant flask, followed by the addition of 5 mL of chlorobenzene. The mixture was reacted at 105 °C for 24 hours under argon protection. After the reaction was complete, the crude product was purified by column chromatography (petroleum ether / dichloromethane v / v = 10:1) to give compound 40 in 80% yield.

[0076] (2) Synthesis of compound 41 In a 50 mL two-necked flask, DCE (5 mL) and DMF (2 mL) containing dissolved compound 40 (138 mg, 0.2 mmol) were added sequentially. The mixture was cooled to 0 °C under argon protection, and POCl3 (0.15 mL) was added dropwise. The reaction was carried out at 0 °C for 1 hour. The mixture was extracted with dichloromethane and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:2) to give compound 41 in 91% yield.

[0077] (3) Synthesis of M10 Compound 41 (134 mg, 0.18 mmol), compound 6 (110 mg, 0.57 mmol), and pyridine (0.7 mL) were added sequentially to a 50 mL two-necked flask, followed by the addition of 15 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:2) to obtain the target product M10 in 78% yield.

[0078] Comparative Example 3 A symmetrical short-wave infrared receptor molecule, M11, which does not contain a quinone core unit, has the following structural formula: ; The synthesis route is as follows: ; (1) Synthesis of compound 43 Compound 42 (400 mg, 0.58 mmol), PdCl2(PhCN)2 (22 mg, 0.056 mmol), potassium fluoride (86 mg, 1.16 mmol), silver nitrate (197 mg, 1.16 mmol), and DMSO (5 mL) were added sequentially to a 30 mL pressure-resistant flask. The mixture was stirred overnight at 60 °C under argon protection. After cooling to room temperature, the mixture was extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:3) to obtain compound 43 in 60% yield.

[0079] (2) Synthesis of M11 Compound 43 (240 mg, 0.17 mmol), compound 6 (117 mg, 0.6 mmol), and pyridine (0.7 mL) were added sequentially to a 100 mL two-necked flask, followed by the addition of 30 mL of chloroform. The reaction was carried out at 60 °C for 1 hour under argon protection. After the reaction was completed, most of the chloroform was removed by vacuum evaporation. The remaining mixture was then precipitated in methanol, and the precipitated solid was collected and purified by column chromatography (petroleum ether / dichloromethane v / v = 1:2) to obtain the target product M11 in 83% yield.

[0080] Test case The OPD devices of the above embodiments (M1~M8) and comparative examples (M9~M11) were fabricated and their basic performance was characterized (the test results are shown in the figure). Figure 2-13 (See Table 1) to illustrate its application in shortwave infrared organic photodetectors.

[0081] The organic photodetector structure is ITO / PEDOT:PSS / active layer / PFN-Br / Al, see Figure 1 As shown in the figure. The specific fabrication method of the organic photodetector is as follows: PEDOT:PSS is deposited on an ITO substrate and annealed at 150°C for 15 minutes to obtain an electron blocking layer (EBL). Then, a blended photoactive layer of polymer donor PTB7-Th and small molecule acceptor prepared in the examples / comparative examples (mass ratio of PTB7-Th to small molecule acceptor is 1:1.2, thickness is about 100 nm) is spin-coated and thermally annealed at 100°C for 10 minutes. Then, PFN-Br is deposited on the active layer to form a hole blocking layer (HBL). Finally, an 80 nm thick Al layer is evaporated on top of the HBL under vacuum conditions through a shadow mask, thus completing the fabrication of the device. The structural formula of PTB7-Th is shown in the figure.

[0082] The EQE and dark current of the aforementioned organic photodetector were measured at a bias voltage of -0.1V, and the corresponding responsivity R and specific detectivity D were calculated. *The responsivity R is the ratio of the photocurrent of the photodetector to the intensity of the incident light, measured in A / W, and is calculated using the following formula: ; in h It is Planck's constant. c It's the speed of light. q It is the absolute value of the electron charge. λ It is the wavelength of light.

[0083] Detectability D * Jones is an indicator that measures the ability of a detector to detect the smallest incident light signal. The unit is Jones, and its calculation formula is as follows: ; in Sn It is the noise spectral density. A It is the area of ​​the active layer of the device. B It measures bandwidth.

[0084] Overall, the asymmetric short-wave infrared receptor small molecule based on a quinone core unit disclosed in this invention has a significant photoresponse in the short-wave infrared band. The organic photodetector device prepared based on the N-type organic molecule disclosed in this invention has achieved a high level in core parameters such as dark current, responsivity, and specific detectivity, making it more suitable for application in unique environments such as flexible sensing, bioimaging, and nighttime surveillance.

[0085] Table 1. Dark current, EQE, responsivity, and specific detectivity for test cases M1~M11

[0086] Figure 2 Dark current density curves of organic photodetectors fabricated using M1, M2, M3, and M9.

[0087] Figure 3 Dark current density curves of organic photodetectors fabricated using M4, M5, M6, and M10.

[0088] Figure 4 Dark current density curves of organic photodetectors fabricated using M7, M8, and M11.

[0089] Figure 5 The external quantum efficiency curves of organic photodetectors fabricated using M1, M2, M3, and M9 are shown.

[0090] Figure 6 External quantum efficiency curves of organic photodetectors fabricated using M4, M5, M6, and M10.

[0091] Figure 7 External quantum efficiency curves of organic photodetectors fabricated using M7, M8, and M11.

[0092] Figure 8 The responsivity curves of the organic photodetectors fabricated using M1, M2, M3, and M9 are shown.

[0093] Figure 9 The responsivity curves of the organic photodetectors fabricated using M4, M5, M6, and M10 are shown.

[0094] Figure 10 The responsivity curves of organic photodetectors fabricated using M7, M8, and M11 are shown.

[0095] Figure 11 The detectivity curves of the organic photodetectors fabricated using M1, M2, M3, and M9 at -0.1V are shown.

[0096] Figure 12 The detectivity curves of the organic photodetectors fabricated using M4, M5, M6, and M10 at -0.1V are shown.

[0097] Figure 13 The detectivity curves of the organic photodetectors fabricated using M7, M8, and M11 at -0.1V are shown.

[0098] This invention designs an asymmetric, non-covalent fused-ring molecule with an A-π1-Q-π2-A structure. The electron-accepting core in the middle and the electron-withdrawing unit at the ends are connected by electron-donating units, which facilitates intramolecular charge transfer and thus broadens the absorption spectral range. Detectors fabricated based on this material exhibit excellent device performance in the near-infrared region, and have significant research value and broad application prospects in OPD and other fields.

[0099] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A kind of asymmetric short-wave infrared receptor small molecule based on quinoid core unit, structural formula is as follows: ； wherein B is quinoid core unit; Pi1, pi2 is bridging unit; A is electron-withdrawing unit.

2. The non-symmetrical short-wave infrared receptor small molecule based on a quinoid core unit according to claim 1, characterized in that, The quinoid core unit is selected from one of the following structural formula: ； Wherein, Y is any one of oxygen, sulfur, selenium; R1, R2, R3 are independently any one of C1-C30 substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ester group.

3. The non-symmetrical shortwave infrared receptor small molecule based on a quinoid core unit according to claim 1, characterized in that, The bridging unit is selected from one of the following structural formula: ； Wherein, X is any one of hydrogen, fluorine, chlorine, bromine, iodine, cyano and trifluoromethyl; Y is any one of oxygen, sulfur and selenium; Z is any one of carbon, silicon and germanium; R4-R9 are independently any one of C1-C16 substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted ester group.

4. The non-symmetrical shortwave infrared acceptor small molecule based on quinoid core unit according to claim 1, characterized in that, The electron-withdrawing unit is selected from one of the following structural formula: ； Wherein, X1, X2, X3, X4, X5, X6 are independently any one of hydrogen, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, C1-C8 substituted or unsubstituted alkyl, C1-C8 substituted or unsubstituted alkoxy, C1-C8 substituted or unsubstituted alkylthio, C1-C8 substituted or unsubstituted silyl, C1-C8 substituted or unsubstituted aryl, C1-C8 substituted or unsubstituted heteroaryl, C1-C8 substituted or unsubstituted ester group.

5. A process for the preparation of the non-symmetrical short-wave infrared acceptor small molecule based on a quinoid core unit according to any one of claims 1 to 4, characterized in that, Comprising the following steps: Step 1, the monomer of quinoid core unit is reacted with the monomer of bridging unit in the presence of catalyst to obtain intermediate; Step 2, the intermediate is reacted with the monomer of electron-withdrawing unit to obtain the asymmetric short-wave infrared receptor small molecule based on quinoid core unit.

6. The production method according to claim 5, characterized by, The molar ratio of the monomer of quinoid core unit to the monomer of each bridging unit is 1:1-1:1.

5. 7.The asymmetric short-wave infrared receptor small molecule based on quinoid core unit according to any one of claims 1-4 is applied in an organic photodetector.

8. An organic photodetector, comprising: The asymmetric short-wave infrared receptor small molecule based on quinoid core unit according to any one of claims 1-4 is included.

9. The organic photodetector of claim 8, wherein, The photosensitive layer contains the asymmetric short-wave infrared receptor small molecule based on quinoid core unit.

10. The organic photodetector of claim 8, wherein, It also includes a hole transport layer and / or an electron transport layer.

Images