Aza-fused ring organic semiconductor compound containing aromatic ring substituted side chain and preparation method and application thereof

Abstract

This invention provides a nitrogen-containing fused-ring organic semiconductor compound with aromatic ring-substituted side chains, its preparation method, and its applications. The compound has the structure shown in Formula I. This application achieves control over molecular conformation, intermolecular interactions, and solid-state thin film stacking behavior by introducing aromatic ring-substituted side chains into the nitrogen-containing fused-ring backbone structure, thereby obtaining organic semiconductor materials suitable for organic optoelectronic devices.

Description

Technical Field

[0001] This invention relates to the field of organic semiconductor materials technology, specifically to a nitrogen-containing heterocyclic organic semiconductor compound with aromatic ring-substituted side chains and its preparation method. Background Technology

[0002] Organic semiconductor materials are a class of organic functional materials that achieve charge transport based on π-conjugated molecules or polymers. They possess characteristics such as molecular designability, tunable energy levels, and flexible fabrication capabilities, and have been widely used in devices such as photodetectors, organic field-effect transistors, and organic solar cells. In these devices, the electronic structure, molecular packing, and solid film morphology of organic semiconductor materials have a significant impact on their carrier transport performance and photoelectric conversion behavior.

[0003] Small-molecule organic semiconductor materials have attracted continuous attention due to their advantages such as well-defined molecular structures, good batch-to-batch consistency, and the ability to control energy levels and stacking characteristics through main-chain or side-chain structures. Existing nitrogen-containing fused-ring organic semiconductor acceptor materials typically use alkyl chains or simple substituents as side chains to improve solubility and processing performance. However, such side chains have limited effect on regulating intermolecular π-π interactions, molecular orientation, and thin film structural stability, and can easily lead to insufficient molecular stacking order and increased conformational disorder in solid films, thereby affecting carrier transport performance and device operational stability.

[0004] Therefore, how to achieve synergistic control over the stacking behavior, conformational stability, and electronic structure of nitrogen-containing fused ring organic semiconductor molecules through reasonable side-chain engineering remains one of the technical problems that urgently need to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing nitrogen-containing fused-ring organic semiconductor acceptor materials in terms of molecular stacking regulation, conformational stability, and thin film morphology control, this invention provides a nitrogen-containing fused-ring organic semiconductor compound with aromatic ring-substituted side chains and its preparation method. By introducing aromatic ring-substituted side chains into the nitrogen-containing fused-ring backbone structure, the molecular conformation, intermolecular interactions, and solid-state thin film stacking behavior can be regulated, thereby obtaining organic semiconductor materials suitable for organic optoelectronic devices.

[0006] One aspect of the present invention provides a nitrogen-containing heterocyclic organic semiconductor compound with aromatic ring-substituted side chains, said compound having the structural formula shown in Formula I: Formula I Wherein, R is selected from C1~C 30 Alkyl, C1~C 30 Substituted alkyl groups, C4~C 20 aryl, C4~C 20One of the substituted aryl groups; Wherein, the substituent of the substituted aryl group is selected from one of alkyl, haloalkyl, alkoxy, haloalkoxy, halogen, alkylthio, and haloalkylthio; Optionally, in the R group, the substituents in the C1-C30 substituted alkyl groups are selected from halogens.

[0007] Preferably, R is selected from any one of the following: C1-C28 straight-chain alkyl, C3-C30 branched alkyl, C1-C28 straight-chain fluorinated alkyl, C3-C30 branched fluorinated alkyl, C4-C20 alkyl aromatic, C4-C20 fluorinated alkyl aromatic, C4-C20 alkoxy aromatic, C4-C20 fluorinated alkoxy aromatic, C4-C20 alkylthio aromatic, C4-C20 fluorinated alkoxy aromatic, C4-C20 aromatic, and C4-C20 fluorinated aromatic.

[0008] Preferably, R is selected from any one of the following: C1-C20 straight-chain alkyl, C3-C20 branched alkyl, C1-C20 straight-chain fluorinated alkyl, C3-C20 branched fluorinated alkyl, C4-C20 alkyl aromatic, C4-C20 fluorinated alkyl aromatic, C4-C20 alkoxy aromatic, C4-C20 fluorinated alkoxy aromatic, C4-C20 alkylthio aromatic, C4-C20 fluorinated alkoxy aryl, C4-C20 aromatic, and C4-C20 fluorinated aromatic.

[0009] More preferably, R is selected from any one of the following: C1-C12 straight-chain alkyl, C3-C12 branched alkyl, C1-C12 straight-chain fluorinated alkyl, C3-C12 branched fluorinated alkyl, C4-C12 alkyl aromatic, C4-C12 fluorinated alkyl aromatic, C4-C12 alkoxy aromatic, C4-C12 fluorinated alkoxy aromatic, C4-C12 alkylthio aromatic, C4-C12 fluorinated alkoxy aromatic, C4-C12 aromatic, and C4-C12 fluorinated aromatic.

[0010] Optionally, X1 and X2 are independently selected from O, S, Se or Te.

[0011] EG1 and EG2 are independently selected from those having the structure shown in Formula II; where the dashed lines in Formula II represent double bond connection positions; Formula II Optionally, Ar' is selected from C4~C 20 aryl, C4~C 30 Substituted aryl, C3~C 20 heteroaryl, C3~C 30 Substituted heteroaryl groups.

[0012] Preferably, Ar' is selected from C4~C 20 aryl, C4~C 30 Substituted aryl, C3~C 20 heteroaryl, C3~C 30 Substituted heteroaryl groups.

[0013] More preferably, Ar' is selected from aryl groups of C4-C6, substituted aryl groups of C4-C6, heteroaryl groups of C3-C6, and substituted heteroaryl groups of C3-C6.

[0014] Optionally, the aryl group is a monocyclic aryl, bicyclic aryl, or tricyclic aryl.

[0015] Optionally, the heteroaryl group is a monocyclic heteroaryl group or a bicyclic heteroaryl group.

[0016] Optionally, the heteroaryl group comprises 5 to 10 skeletal cyclic atoms, wherein at least one cyclic atom is a heteroatom selected from sulfur atoms.

[0017] Optionally, the substituents of the substituted aryl and substituted heteroaryl groups are independently selected from any one of alkyl halogens, cyano groups, ester groups, alkyl groups, alkoxy groups, and alkylthio groups.

[0018] Optionally, A is selected from , One of them.

[0019] Preferably, EG1 and EG2 are independently selected from any of the following structural formulas.

[0020] .

[0021] Optionally, R1, R2, R3, R4, R5, R6, R7, and R8 are independently selected from hydrogen atoms, halogens, cyano groups, and C1~C6 groups. 20 Alkyl, C1~C 20 Alkoxy, C1~C 20 Alkylthio, C1~C 20 Any of the ester groups.

[0022] Optionally, EG1 and EG2 are electron-withdrawing units; EG1 and EG2 are derived from EG compounds, and the EG compounds are selected from one of the indigo ketone derivatives.

[0023] Optionally, the EG compound is selected from one of 5,6-difluoro-3-(dicyanomethylene)indoketone, 6-fluoro-3-(dicyanomethylene)indoketone, 5,6-dichloro-3-(dicyanomethylene)indoketone, and 3-(dicyanomethylene)indoketone.

[0024] Optionally, Ar1 is selected from one of C4-C20 aromatic groups and C4-C20 substituted aromatic groups; wherein the substituents in the C4-C20 substituted aromatic groups are selected from any one of fluorinated alkyl groups, alkoxy groups, fluorinated alkoxy groups, alkylthio groups, fluorinated alkylthio groups, and halogens.

[0025] Preferably, Ar1 is independently selected from any one of the structures shown in Formula III-1 and Formula III-2.

[0026] Formula III-1 Formula III-2 Optionally, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 Independently selected from hydrogen atoms, halogens, C1~C 20 alkyl chain, C1~C 20 Fluorinated alkyl chains, C1~C 20 alkoxy chain, C1~C 20 Fluorinated alkoxy chains, C1~C 20 alkylthioyl chain, C1~C 20 Any of the fluorinated alkyl thioyl chains, with the dashed lines indicating the connection positions of the groups.

[0027] Optionally, X3 is independently selected from O, S, Se or Te.

[0028] Optionally, Ar2 and Ar3 are independently selected from C4~C 20 The aryl group contains at least one thiophene ring that forms a fused ring with the pyrrole ring in Formula I.

[0029] Preferably, Ar2 and Ar3 are independently selected from any one of the structures shown in Formula IV-1 and Formula IV-2.

[0030] Formula IV-1 Formula IV-2 Optionally, R 15 R 16 Independently selected from hydrogen atoms, C1~C 20 alkyl chain, C1~C 20 alkoxy chain, C1~C 20 alkylthioyl chain, C1~C 20 carbonyl group, C1~C 20 Any of the ester groups, with the dashed lines indicating the connection positions of the groups.

[0031] Preferably, Ar2 and Ar3 are thiophene rings that form fused rings with the pyrrole ring in Formula I.

[0032] A second aspect of the present invention provides a method for preparing a nitrogen-containing heterocyclic fused-ring organic semiconductor compound having the structure shown in formula (I), the method comprising at least the following steps: (1) The oxidation reaction of compound 1 yields compound 2. The material containing compound 1 is oxidized with an oxidizing agent in a suitable solvent to obtain a material containing compound 2. The reaction can be carried out in dichloromethane, acetonitrile, or water, and compound 2 can be obtained by stirring the reaction mixture.

[0033]

[0034] Compound 1

[0035] Compound 2 (2) The acetal reaction of compound 2 yields compound 3. The material containing compound 2 is reacted with neopentyl glycol and an acidic catalyst (such as p-toluenesulfonic acid or mesitylenesulfonic acid) in a suitable solvent to produce a material containing compound 3. The solvent can be benzene or toluene.

[0036]

[0037] Compound 3 (3) Compound 3 undergoes nucleophilic addition / reduction / acetal hydrolysis and other reactions to give compound 4. The material containing compound 3 is reacted with a material containing an aromatic ring substituent Ar1, n-butyllithium, stannous chloride, and hydrochloric acid solution to generate a material containing compound 4. The reaction may include nucleophilic addition, reduction, and acetal hydrolysis, or combinations thereof.

[0038]

[0039] Compound 4 (4) The Knoevenagel condensation reaction of compound 4 yields the target product I. The material containing compound 4 and the material containing EG end-group compounds were subjected to a Knoevenagel condensation reaction in the presence of a suitable solvent and a basic acid-binding agent to obtain the target compound having the structure shown in Formula I. EG1 and EG2 are electron-withdrawing units derived from EG compounds (such as indigo ketone derivatives).

[0040] Optionally, the reaction in step (1) is an oxidation reaction, the reaction solvent is selected from at least one of dichloromethane, acetonitrile or water, and the oxidant is selected from at least one of cerium ammonium nitrate or cerium ammonium sulfate; the molar ratio of the oxidant to the compound 1 is (1 to 6.0):1, the reaction temperature is 25 to 100°C, and the reaction time is 6 to 48 hours.

[0041] Optionally, the oxidant is selected from cerium ammonium nitrate and / or cerium ammonium sulfate.

[0042] Optionally, the upper limit of the molar ratio of the oxidant to compound 1 can be independently selected from 6:1, 5.5:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, and 1:1, and the lower limit can be independently selected from 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, and 1:2.0; the upper limit of the reaction temperature can be independently selected from 100℃, 90℃, 80℃, 70℃, 60℃, and 50℃, and the lower limit can be independently selected from 25℃, 30℃, 35℃, 40℃, 45℃, and 50℃; the upper limit of the reaction time can be independently selected from 48 hours, 46 hours, 44 hours, 42 hours, 40 hours, 38 hours, and 36 hours. The timeframes are 1 hour, 34 hours, 32 hours, 30 hours, and 28 hours. The lower limit can be independently selected from 6 hours, 8 hours, 10 hours, 14 hours, 16 hours, 20 hours, 24 hours, and 28 hours.

[0043] Optionally, the reaction in step (2) is an acetal reaction, the reaction temperature is 25-110℃, and the reaction time is 5-24 hours; the reaction solvent is selected from at least one of benzene or toluene; the catalyst is selected from at least one of p-toluenesulfonic acid or mesitylenesulfonic acid, and the amount of catalyst added is 1%-10% of the molar amount of compound 2; the molar ratio of compound 2 to neopentyl glycol is 1:(5-12).

[0044] Optionally, the upper limit of the reaction temperature can be independently selected from 110℃, 100℃, 90℃, 80℃, 70℃, and 60℃, and the lower limit can be independently selected from 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, and 60℃; the upper limit of the reaction time can be independently selected from 24 hours, 23 hours, 22 hours, 21 hours, 20 hours, 19 hours, 18 hours, 17 hours, 16 hours, 15 hours, 14 hours, 13 hours, 12 hours, 11 hours, and 10 hours, and the lower limit can be independently selected from 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, and 10 hours; the catalyst addition amount, based on the molar amount of compound 2, can have an upper limit independently selected from 10%, 9%, 8%, 7%, 6%, and 5%, and a lower limit independently selected from 1%, 2%, 3%, 4%, and 5%; the compound 2 The upper limit of the molar ratio with neopentyl glycol can be independently selected from 1:12, 1:11, 1:10, 1:9, and 1:8, and the lower limit can be independently selected from 1:5, 1:6, 1:7, and 1:8.

[0045] Optionally, the reaction in step (3) includes at least one or a combination of nucleophilic addition, reduction, and acetal hydrolysis; the reaction temperature is -100℃ to 100℃, and the reaction time is 5 to 12 hours; the reaction solvent is selected from at least one of tetrahydrofuran, diethyl ether, or water. In some embodiments, the reaction reagents include compound 3, compound Ar1, n-butyllithium, stannous chloride, and hydrochloric acid solution; wherein the molar ratio of compound 3 to compound Ar1 is 1:(4 to 10), the molar ratio of compound Ar1 to n-butyllithium is 1:(1 to 3), and the molar ratio of stannous chloride to compound 3 is 1:(4 to 10).

[0046] Optionally, the upper limit of the reaction temperature can be independently selected from 100℃, 80℃, 60℃, 40℃, 20℃, and 0℃, and the lower limit can be independently selected from -100℃, -80℃, -60℃, -40℃, -20℃, and 0℃; the upper limit of the reaction time can be independently selected from 12 hours, 11 hours, 10 hours, 9 hours, 8 hours, and 7 hours, and the lower limit can be independently selected from 5 hours, 6 hours, and 7 hours; the compound 3 The upper limit of the molar ratio of compound Ar1 to compound Ar1 can be independently selected from 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, and the lower limit can be independently selected from 1:4, 1:5, 1:6; the upper limit of the molar ratio of compound Ar1 to n-butyllithium can be independently selected from 1:3, 1:2, 1:1.5, and the lower limit can be independently selected from 1:1; the upper limit of the molar ratio of stannous chloride to compound 3 can be independently selected from 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, and the lower limit can be independently selected from 1:4, 1:5.

[0047] Optionally, the Knoevenagel reaction in step (4) is a condensation reaction, with a reaction temperature of 50–70°C and a reaction time of 8–24 hours; the reaction solvent is selected from at least one of chloroform, chlorobenzene, or 1,2-dichloroethane; the acid-binding agent for the condensation reaction includes pyridine. In some embodiments, the molar ratio of compound 5 to end-group compound EG is 1:(5–12). The end-group compound EG includes indigo ketone compounds containing a dicyanomethylene structure, and the end-group compounds EG1 and EG2 are each independently selected from at least one of 5,6-difluoro-3-(dicyanomethylene)indigo ketone, 6-fluoro-3-(dicyanomethylene)indigo ketone, and 5,6-dichloro-3-(dicyanomethylene)indigo ketone.

[0048] Optionally, the upper limit of the reaction temperature can be independently selected from 70℃, 65℃, 60℃, and 55℃, and the lower limit can be independently selected from 50℃, 55℃, and 60℃; the upper limit of the reaction time can be independently selected from 24 hours, 22 hours, 20 hours, 18 hours, 16 hours, 14 hours, 12 hours, and 10 hours, and the lower limit can be independently selected from 8 hours, 10 hours, and 12 hours; the upper limit of the molar ratio of compound 5 to terminal compound EG can be independently selected from 1:12, 1:11, 1:10, 1:9, and 1:8, and the lower limit can be independently selected from 1:5, 1:6, 1:7, and 1:8.

[0049] A third aspect of the present invention provides a receptor material comprising, in any proportion, an aromatic ring-substituted side chain-containing nitrogen-containing fused-ring organic semiconductor compound as described in any of the foregoing technical solutions, or comprising at least one of the aromatic ring-substituted side chain-containing nitrogen-containing fused-ring organic semiconductor compounds prepared by the foregoing methods.

[0050] A fourth aspect of the present invention provides a semiconductor material comprising the acceptor material and may further comprise a donor material, additives or other functional components.

[0051] In this application, all conditions involving numerical ranges can be independently selected from any point value within the selected value range, including the range endpoint values.

[0052] In this application, all conditions involving numerical ranges can be independently selected from any point value within the selected value range, including the range endpoint values.

[0053] In this application, C1 to C30, C4 to C20, C3 to C30, etc., all represent the range of the number of carbon atoms contained in the corresponding group. For example, alkyl groups of C1 to C30 refer to alkyl groups with 1 to 30 carbon atoms.

[0054] In this application, the terms C3-C30 branched alkoxy, C3-C30 branched fluorinated alkoxy, C3-C30 branched alkylthio, C3-C30 branched fluorinated alkylthio, C3-C30 branched alkyl group, and C3-C30 branched fluorinated alkyl group all refer to alkyl groups having at least one branch, and the branching position of the branch can be on any carbon atom from C1 to C29.

[0055] In this application, alkyl refers to a group formed by the loss of any hydrogen atom from an alkane compound, and the alkane compound includes straight-chain alkanes, branched-chain alkanes, and cycloalkanes.

[0056] In this application, haloalkyl refers to a group formed by replacing at least one hydrogen atom on an alkyl group with a halogen atom.

[0057] In this application, aryl is a group formed by losing any hydrogen atom on the aromatic ring in an aromatic compound molecule; the aromatic compound includes compounds containing an aromatic ring and compounds in which at least one hydrogen atom on the aromatic ring is replaced by an alkyl group.

[0058] In this application, the term "heteroaryl" as used alone or in combination herein refers to an arbitrarily substituted heteroaryl group comprising about 5 to 20 skeletal cyclic atoms, for example 5 to 12 or 5 to 10 skeletal cyclic atoms, wherein at least one (e.g., 1 to 4, 1 to 3, or 1 to 2) cyclic atom is a heteroatom, which is sulfur, but not limited thereto; the ring of the group does not contain two adjacent O or S atoms. A heteroaryl group can be a monocyclic heteroaryl (having one ring), a bicyclic heteroaryl (having two rings), or a polycyclic heteroaryl (having more than two rings). In embodiments where two or more heteroatoms appear in the ring, the two or more heteroatoms may be identical or may be partially or entirely different. A bicyclic or polycyclic heteroaryl group can be formed by fusion of a monocyclic heteroaryl group with other independent rings (such as aromatic rings or aromatic heterocycles) (collectively referred to as fused cyclic heteroaryl groups). Non-limiting examples of monocyclic heteroaryl groups include monocyclic heteroaryl groups having 5 to 12, 5 to 10, 5 to 7, or 6 skeletal cyclic atoms, such as thiophene groups; fused cyclic heteroaryl groups include bicyclic thiophene groups.

[0059] In this application, the alkoxy group is a group formed in an alkyl alcohol molecule after losing a hydrogen atom from the hydroxyl group.

[0060] In this application, the alkylthio group is a group formed after the loss of a hydrogen atom from the thiol group in an alkylthiol molecule.

[0061] In this application, the haloalkylthio group is a group in which at least one hydrogen atom of the alkylthio group is replaced by a halogen atom.

[0062] In this application, haloalkylthioaromatic group refers to a group in which at least one hydrogen atom on the alkylthio group is replaced by a halogen atom.

[0063] In this application, the ester group refers to the functional group of the ester in a carboxylic acid derivative, with the structural formula -COOR, where R is a non-hydrogen group such as an alkyl group.

[0064] Compared with the prior art, the beneficial effects of the present invention are: Compared with the prior art, the nitrogen-containing fused ring organic semiconductor compound with aromatic ring-substituted side chains provided by the present invention achieves effective control over molecular conformation, intermolecular interactions and solid film stacking behavior by introducing aromatic ring-substituted side chains into the nitrogen-containing fused ring main chain structure.

[0065] Specifically, the aromatic ring substitution of the side chain is beneficial to enhancing the π-π interaction between molecules, improving the orderliness and structural stability of molecular stacking, and at the same time, it helps to form a structurally stable and reproducible film morphology without significantly reducing the solubility and processing performance.

[0066] Furthermore, the nitrogen-containing fused-ring organic semiconductor compounds provided by this invention exhibit excellent tunability in energy level distribution and optical band gap, which is beneficial for their application as electron acceptor materials in organic optoelectronic devices. Acceptor materials, semiconductor materials, and photoactive film materials constructed based on these compounds can be applied to a variety of organic optoelectronic devices, including organic solar cells, organic field-effect transistors, and photodetectors. Attached Figure Description

[0067] Figure 1 The intermediate compound 3a prepared in Example 1 1 H NMR spectrum.

[0068] Figure 2 The intermediate compound 3b prepared in Example 2 1 H NMR spectrum.

[0069] Figure 3 The intermediate compound 3c prepared in Example 3 1 H NMR spectrum.

[0070] Figure 4 The organic semiconductor of type IA prepared in Example 1 1 H NMR spectrum.

[0071] Figure 5 The organic semiconductor IB prepared in Example 2 1 H NMR spectrum.

[0072] Figure 6The organic semiconductor IC prepared in Example 3 1 H NMR spectrum.

[0073] Figure 7 The image shows the HR-MS spectrum of the organic semiconductor IA prepared in Example 1.

[0074] Figure 8 The image shows the UV-vis absorption spectrum of the organic semiconductor IA prepared in Example 1 in the thin film state.

[0075] Figure 9 The image shows the UV-vis absorption spectrum of the organic semiconductor IB prepared in Example 2 in the thin film state.

[0076] Figure 10 This is a current-voltage (JV) curve of a solar cell device fabricated using PM6: formula IA as the active layer.

[0077] Figure 11 This is a current-voltage (JV) curve of a solar cell device fabricated with PM6: IB as the active layer.

[0078] Figure 12 This is a current-voltage (JV) curve of a solar cell device fabricated using PM6: IC as the active layer. Detailed Implementation

[0079] To better illustrate the content of this invention, the technical solution of this invention will be further explained below through specific embodiments, including material synthesis and characterization, device fabrication and performance testing, etc.

[0080] Unless otherwise specified, all raw materials, catalysts, and other chemical reagents involved in the embodiments of this application are commercially available products.

[0081] The materials were tested using a Bruker AVANCE-400 nuclear magnetic resonance spectrometer. 1 1H NMR spectra; mass spectra were measured using an IonSpec 4.7T Fourier transform mass spectrometer from IonSpec Corporation, USA.

[0082] Example 1: Preparation of compound IA This embodiment provides a preparation route for a representative compound of Formula I (hereinafter referred to as Formula IA). In Formula IA: R is 2-butyloctyl; Ar1 ​​is... ;EG is selected from X1 and X2 are selected from S; Ar2 and Ar3 are thiophene.

[0083] This compound is only a representative embodiment of the present invention, and its structure does not constitute a limitation on the scope of Formula I.

[0084] The preparation of intermediate M36-CHO is known to be found in Angew. Chem. Int. Ed. 2020, 59, 21627.

[0085] (1) Oxidation of M36-CHO to prepare compound a

[0086] In a 100 mL single-necked round-bottom flask, M36-CHO (500 mg, 0.438 mmol), 5 mL of deionized water, and 20 mL of acetonitrile were added. Cerium ammonium nitrate (1.44 g, 2.63 mmol, substrate molar ratio approximately 1:6) was weighed and slowly added to the reaction mixture under magnetic stirring at room temperature. The reaction was continued at room temperature (25 °C) for 6 h. After the reaction was complete, the mixture was extracted with dichloromethane (3 × 30 mL), and the organic layers were combined, dried, and evaporated to dryness to obtain the crude product. Purification was performed by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 1:1 → 0:1) to obtain a red solid compound 1a (240 mg, yield 68%). ¹H NMR (400 MHz, CDCl3, δ): 9.87 (s, 2H), 7.58 (s, 2H), 4.73 (d, δ). J = 8.0 Hz, 4H), 1.91 (m, 2H), 1.29-1.14 (m, 32H), 0.83-0.78 (m, 12H).

[0087] (2) Preparation of compound 2a by acetal reaction of compound 1a

[0088] Compound 1a (100 mg, 0.125 mmol) and 10 mL of toluene were added to a 50 mL single-necked flask, and the mixture was purged with nitrogen three times at room temperature. Then, neopentyl glycol (129.7 mg, 1.25 mmol) and p-toluenesulfonic acid (2.14 mg, 0.0124 mmol) were added, and the mixture was heated to reflux and reacted for 12 h. After cooling, the reaction mixture was quenched with methanol, and the solution was filtered to obtain a red solid (117 mg). This solid did not require further purification and was used directly in the next reaction step.

[0089] (3) Preparation of compound 3a by nucleophilic addition / reduction / acetal hydrolysis of compound 2a

[0090] Under ice bath (0 °C) conditions, 2.5 M, 0.41 mL of n-butyllithium was added dropwise to a tetrahydrofuran solution of 2-(2-butyloctyl)thiophene (258 mg, 1.03 mmol), and stirring was continued for 1 h after the addition was complete. Compound 2a (100 mg, 0.103 mmol) was then rapidly added, and the reaction was heated to 50 °C for 1 h, followed by cooling to room temperature. SnCl₂·2H₂O (231 mg, 1.03 mmol) was dissolved in 10% HCl (4 mL) and added to the above reaction solution, and the reaction was continued at room temperature for 12 h. After the reaction was complete, the mixture was extracted with dichloromethane (3 × 30 mL), the organic layer was collected, evaporated to dryness, and purified by silica gel column chromatography (petroleum ether:dichloromethane = 1:1) to give a red oily substance 3a (85 mg, 65%). ¹H NMR (400 MHz, CDCl3, δ): 9.87 (s, 2H), 7.55 (s, 2H), 3.38 (dd, J1=116 Hz, J2=156 Hz, 4H), 2.88 (d, J = 8.0 Hz, 4H), 2.00 (m, 2H), 1.31–1.23 (m, 64H), 0.91–0.84 (m, 24H), such as Figure 1 As shown.

[0091] (4) Knoevenagel condensation of compound 3a to prepare compound IA

[0092] Compound 3a (80 mg, 0.063 mmol) was added to anhydrous chloroform (10 mL), followed by 0.5 mL of pyridine. The reaction was carried out at 50 °C for 8 h. After cooling to room temperature, a large amount of methanol was added to precipitate the product, which was then purified by silica gel column chromatography to give a blue solid of formula IA (73 mg, 68% yield). ¹H NMR (400MHz, CDCl3, δ): 9.89 (s, 2H), 8.51 (dd, J1= 4.00 Hz, J2= 9.2 Hz, 2H), 7.77 (m, 2H), 7.66 (t, J = 8.00 Hz, 2H), 7.41 (m, 2H), 7.00 (m, 2H), 3.28 (m, 4H), 2.91 (m, 4H), 1.72 (m, 4H), 1.41–0.89 (m, 64H), 0.85–0.59 (m, 24H), such as Figure 4 As shown. High-resolution mass spectrometry (HR-MS): Calculated value: C 100 H 112N6O2S4F4 = 1697.714; Measured value: 1697.714, the result is as follows. Figure 7 As shown.

[0093] Example 2: Preparation of Compound IB To further illustrate the versatility of the present invention, this embodiment provides another representative compound with the formula IB: Ar1. Other structural parameters are consistent with those of Formula IA in Example 1. Formula IB is also a representative compound of Formula I and does not constitute a limitation on the scope of protection of this invention.

[0094] (1) M36-CHO was modified to obtain compound 3b

[0095] Similar to Example 1, except that the reaction substrate was replaced with 2-(2-butyloctyl)-3-fluorothiophene, and the remaining steps (acetal, nucleophilic addition, reduction) were the same as in Example 1. The final product was a red oily compound 3b (90 mg, 67%). ¹H NMR (400 MHz, CDCl₃, δ): 9.89 (s, 2H), 7.58 (s, 2H), 3.35 (dd, J = 116 / 156 Hz, 4H), 2.83 (d, J = 8.0 Hz, 4H), 1.72 (m, 2H), 1.46–0.94 (m, 64H), 0.87–0.57 (m, 24H), as shown. Figure 2 .

[0096] (2) Compound 3b condenses with the end group of indigo ketone to obtain formula IB

[0097] The procedure was consistent with the Knoevenagel condensation in Example 1. The final result was a blue solid, IB (80 mg, 67%). ¹H NMR (400 MHz, CDCl₃, δ): 9.89 (s, 2H), 8.51 (dd, J = 4.0 / 9.2 Hz, 2H), 7.80 (m, 2H), 7.68 (t, J = 8.0 Hz, 2H), 7.21 (d, J = 72 Hz, 2H), 3.36 (dd, J = 120 / 160 Hz, 4H), 2.86 (m, 4H), 1.73 (m, 4H), 1.49–1.20 (m, 24H), 1.19–0.57 (m, 64H), as shown. Figure 5 As shown.

[0098] Example 3: Preparation of Formula IC Compound This embodiment further provides another representative compound of Formula I (hereinafter referred to as Formula IC) to illustrate the universality of the present invention.

[0099] In equation (I)-C: Ar1 is Other structural parameters are consistent with Formula IA in Example 1. It should be understood that Formula (I)-C is only an exemplary structure of the compound of Formula (I), and its specific configuration does not limit the scope of protection of the present invention.

[0100] (1) M36-CHO was modified to obtain compound 3c

[0101] Consistent with steps (1)–(3) of Example 1, except that the aryl lithium precursor used for the nucleophilic addition was replaced with 2-(2-butyloctyl)-3-chlorothiophene, and the remaining reaction conditions (including acetal reaction, nucleophilic addition, reduction and hydrolysis steps) remained unchanged. The final product was a red oily solid compound 3c (87 mg, 63% yield). ¹H NMR (400 MHz, CDCl3, δ): 9.90 (s, 2H), 7.58 (s, 2H), 3.34 (m, 4H), 2.88 (m, 4H), 1.75 (m, 2H), 1.35–1.24 (m, 64H), 0.93–0.82 (m, 24H), as shown. Figure 3 As shown.

[0102] (2) Compound 3c condenses with the indigo ketone end group to obtain formula IC

[0103] The reaction procedure in this step is the same as the Knoevenagel condensation method in Example 1, namely: using compound 3c as the donor skeleton; using 5,6-difluoro-3-(dicyanomethylene)indophenone or the same terminal group EG used in the examples as the electron-withdrawing unit; and carrying out the condensation reaction at 50–70°C in chloroform or chlorobenzene solvent and pyridine as the acid-binding agent until the reaction is complete. After purification (precipitation + column chromatography), a blue solid IC (80 mg, yield 67%) was obtained. ¹H NMR (400 MHz, CDCl3, δ): 9.89 (s, 2H), 8.53 (dd, J1= 4.0 Hz, J2= 9.2 Hz, 2H), 7.82 (m, 2H), 7.69 (t, J = 8.0Hz, 2H), 7.21 (m, 2H), 3.49 (m, 4H), 2.91 (m, 4H), 1.76 (m, 4H), 1.49–1.19 (m, 64H), 0.93–0.83 (m, 24H), such as Figure 6 As shown.

[0104] Example 4: Fabrication of an organic solar cell based on formula IA This embodiment utilizes the organic semiconductor compound IA prepared in Example 1 as an electron acceptor material to fabricate an organic solar cell device, in order to further verify the applicability of the material of the present invention in the photovoltaic field.

[0105] The solar cell device employs a positive-mounted structure: glass substrate / ITO (indium tin oxide) / PEDOT (polyvinyl dioxythiophene):PSS (sodium polystyrene sulfonate) / active layer / PDIN (2,9-bis(3-dimethylaminopropyl)isoquinoline[4′,5′,6′:6,5,10]anthra[2,1,9-def]isoquinoline-1,3,8,10(2H,9H)-tetraone) / silver. The ITO layer is attached to the glass substrate; both ITO and the glass substrate will be referred to as ITO glass. The ITO glass was ultrasonically washed sequentially with detergent, water, acetone, and isopropanol for 30 minutes each. It was then dried overnight at 90°C in an oven. After treating the ITO glass with UV ozone for 15 minutes, PEDOT:PSS was spin-coated onto the ITO layer and placed at 140°C. o Heated in an oven at C for 15 minutes, then quickly transferred to a glove box for later use. Polymer donor PM6 (purchased from Solon Organic Optoelectronics Technology (Beijing) Co., Ltd.) and the organic semiconductor compound IA obtained in Example 1 were dissolved in chloroform at a weight ratio of 1:1. 0.5% (v / v) of 1-chloronaphthalene was added as an additive, resulting in a total solution concentration of 16 mg / mL. The solution was stirred at 50°C for 4 hours, and then spin-coated onto a PEDOT:PSS film as an active layer with a thickness of approximately 100 nm. To improve electron injection efficiency and block holes, a methanol solution of PDIN (1.5 mg / mL containing 0.2% acetic acid) was spin-coated onto the active layer. Finally, the negative electrode of the battery was subjected to a vacuum of approximately 5 × 10⁻⁶. -5 The process was completed under Pa conditions by thermal evaporation of a 100 nm silver electrode, and the device area was 4 mm². 2 .

[0106] Example 5: Organic Solar Cells Based on Type IB The device fabrication process in Example 5 is exactly the same as that in Example 4, except that the active layer material is replaced with PM6:IB = 1:1 (mass ratio). The remaining steps are the same and will not be described again.

[0107] Example 6: Organic Solar Cells Based on IC The device fabrication process in Example 6 is exactly the same as that in Example 4, except that the active layer material is replaced with PM6:IC = 1:1 (mass ratio), and the other steps are the same.

[0108] The commercially available PM6 was purchased from Shuolun Organic Optoelectronics Technology (Beijing) Co., Ltd. M n It is approximately 41 kg / mol, PDI is approximately 2.0, and its structure is as follows:

[0109] Test Example 1 Performance tests were performed on the devices obtained in Examples 4-6: The device was tested using a Keithley 2400 digital source meter under AM 1.5G (100mW / cm2) illumination simulated by an Oriel Sol3A (Newport) solar simulator.

[0110] The parameters of the solar cell devices obtained in Examples 4-6 are summarized in Table 1, including open-circuit voltage ( V oc ), short-circuit current ( J sc The fill factor (FF) and photoelectric conversion efficiency (PCE) are shown in the corresponding current-voltage curves. Figures 10-12 .

[0111] Table 1. Parameters of solar cell devices prepared based on the aforementioned organic semiconductor compounds.

[0112] As can be seen from the table, the aryl structure with different side chain / halogen modifications has a significant impact on photovoltaic performance. In particular, the IB formula with the introduction of fluorine atoms improves the PCE to 12.31%, which is significantly better than the IA formula (1.76%); the IC formula with the introduction of chlorine atoms can also achieve a performance of 9.56%.

[0113] Test Example 2: Characterization of Molecular Optical Absorption Properties Typical examples are selected: Formula IA (Example 1) and Formula IB (Example 2).

[0114] The absorption spectrum of the thin film was measured using a PerkinElmer Lambda 900 UV-Vis-NIR spectrophotometer. The test results are as follows: Figure 8-9 As shown, both Equations IA and IB exhibit a significant π-π* absorption peak in the 600-800 nm range. Both absorptions extend into the near-infrared (NIR) region. Equation (I)-A has an absorption edge reaching 900 nm, making it more advantageous for utilizing the infrared portion of sunlight. Halogen modulation (F, Cl) leads to significant energy level regulation and differences in light absorption, significantly impacting photovoltaic performance.

[0115] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A nitrogen-containing heterocyclic fused-ring organic semiconductor compound with aromatic ring-substituted side chains, characterized in that, The compound has the structure shown in Formula I. Equation I Wherein, R is selected from one of C1-C30 alkyl, C1-C30 substituted alkyl, C4-C20 aryl, and C4-C20 substituted aryl; The substituents in the substituted aryl group are selected from one of alkyl, haloalkyl, alkoxy, haloalkoxy, halogen, alkylthio, and haloalkylthio. X1 and X2 are independently selected from O, S, Se or Te; EG1 and EG2 are independently selected from end base units with the structure shown in Equation II, where the dashed lines in Equation II represent double bond connection positions; Formula II Ar′ is selected from one of C4-C20 aryl, C4-C30 substituted aryl, C3-C20 heteroaryl, and C3-C30 substituted heteroaryl. A is selected from , One of them; Ar1 is selected from one of C4-C20 aromatic groups and C4-C20 substituted aromatic groups; wherein the substituent in the C4-C20 substituted aromatic groups is selected from any one of fluorinated alkyl, alkoxy, fluorinated alkoxy, alkylthio, fluorinated alkylthio, and halogen. Ar2 and Ar3 are independently selected from C4 to C20 aryl groups, and each contains at least one thiophene ring and forms a fused ring structure with the pyrrole ring in Formula I.

2. The compound according to claim 1, characterized in that, In the R group, the substituents in the C1-C30 substituted alkyl group are selected from halogens; Preferably, R is selected from any one of the following: C1-C28 straight-chain alkyl, C3-C30 branched alkyl, C1-C28 straight-chain fluorinated alkyl, C3-C30 branched fluorinated alkyl, C4-C20 alkyl aromatic, C4-C20 fluorinated alkyl aromatic, C4-C20 alkoxy aromatic, C4-C20 fluorinated alkoxy aromatic, C4-C20 alkylthio aromatic, C4-C20 fluorinated alkoxy aromatic, C4-C20 aromatic, and C4-C20 fluorinated aromatic.

3. The compound according to claim 1 or 2, characterized in that, The R is selected from any one of the following: C1-C20 straight-chain alkyl, C3-C20 branched alkyl, C1-C20 straight-chain fluorinated alkyl, C3-C20 branched fluorinated alkyl, C4-C20 alkyl aromatic, C4-C20 fluorinated alkyl aromatic, C4-C20 alkoxy aromatic, C4-C20 fluorinated alkoxy aromatic, C4-C20 alkylthio aromatic, C4-C20 fluorinated alkoxy aromatic, C4-C20 aromatic, and C4-C20 fluorinated aromatic.

4. The compound according to claim 3, characterized in that, The R is selected from any one of the following: C1-C12 straight-chain alkyl, C3-C12 branched alkyl, C1-C12 straight-chain fluorinated alkyl, C3-C12 branched fluorinated alkyl, C4-C12 alkyl aromatic, C4-C12 fluorinated alkyl aromatic, C4-C12 alkoxy aromatic, C4-C12 fluorinated alkoxy aromatic, C4-C12 alkylthio aromatic, C4-C12 fluorinated alkoxy aromatic, C4-C12 aromatic, and C4-C12 fluorinated aromatic. Preferably, Ar′ is a monocyclic aryl, bicyclic aryl, or tricyclic aryl, and / or the heteroaryl is a monocyclic heteroaryl or bicyclic heteroaryl; Preferably, the heteroaryl group comprises 5 to 10 skeletal cyclic atoms, wherein at least one cyclic atom is a heteroatom selected from sulfur atoms; Preferably, the substituents of the substituted aryl and substituted heteroaryl groups are independently selected from any one of alkyl, halogen, cyano, ester, alkyl, alkoxy, or alkylthio groups; Preferably, EG1 and / or EG2 are electron-withdrawing units derived from indigo ketone derivatives of EG compounds; Preferably, EG1 and EG2 are independently selected from any one of the following structural formulas. ； Preferably, R1, R2, R3, R4, R5, R6, R7, and R8 are independently selected from hydrogen atoms, halogens, cyano groups, and C1~C6 groups. 20 Alkyl, C1~C 20 Alkoxy, C1~C 20 Alkylthio, C1~C 20 Any one of the ester groups; Preferably, the EG compound is selected from one or more of 5,6-difluoro-3-(dicyanomethylene)indoketone, 6-fluoro-3-(dicyanomethylene)indoketone, 5,6-dichloro-3-(dicyanomethylene)indoketone, and 3-(dicyanomethylene)indoketone; Preferably, Ar1 is selected from any one of C4-C20 alkyl aromatic group, C4-C20 fluorinated alkyl aromatic group, C4-C20 alkoxy aromatic group, C4-C20 fluorinated alkoxy aromatic group, C4-C20 alkylthio aromatic group, C4-C20 fluorinated alkoxy aromatic group, C4-C20 aromatic group, and C4-C20 fluorinated aromatic group; Preferably, Ar1 is independently selected from any one of the structures shown in Formula III-1 or Formula III-2, wherein the dashed lines in Formula III-1 and Formula III-2 indicate the positions connected to the main chain, R9 to R16 are independently selected from hydrogen, halogen, C1 to C20 alkyl chain, C1 to C20 fluorinated alkyl chain, C1 to C20 alkoxy chain, C1 to C20 fluorinated alkoxy chain, C1 to C20 alkylthio chain or C1 to C20 fluorinated alkylthio chain, and X3 is independently selected from O, S, Se or Te; Formula III-1 Formula III-2; Preferably, Ar2 and Ar3 are independently selected from any one of the structures shown in Formula IV-1 or Formula IV-2, wherein the dashed lines in Formula IV-1 and Formula IV-2 are the connection positions that form a fused ring with the pyrrole ring in Formula I; Formula IV-1 Formula IV-2; Preferably, Ar2 and Ar3 each contain a thiophene ring, which forms a fused structure with the pyrrole ring in Formula I; Preferably, X1 and / or X2 is S.

5. A method for preparing the nitrogen-containing heterocyclic fused-ring organic semiconductor compound with aromatic ring-substituted side chains according to any one of claims 1 to 4, characterized in that, The preparation method includes: (1) The material containing compound 1 is oxidized with an oxidant in dichloromethane, acetonitrile and / or water as solvents to obtain the material containing compound 2; Compound 1 Compound 2 (2) The material containing compound 2 is reacted with neopentyl glycol and a catalyst in benzene and / or toluene to produce a material containing compound 3. Compound 3 (3) The material containing compound 3 is reacted with the material containing Ar1, n-butyllithium, stannous chloride and hydrochloric acid solution in at least one of the following reactions: nucleophilic addition, reduction and acetal hydrolysis, to obtain the material containing compound 4. Compound 4 (4) The material containing compound 4 and the material containing EG compound are subjected to a Knoevenagel condensation reaction in chloroform, chlorobenzene and / or 1,2-dichloroethane to obtain a compound with the structure shown in Formula I, wherein EG1 and EG2 are electron-withdrawing terminal units from the EG compound.

6. The preparation method according to claim 5, characterized in that, In step (1), the molar ratio of the oxidant to compound 1 is (1.0 to 6.0):1, the reaction temperature is 25 to 100°C, and the reaction time is 6 to 48 hours; Preferably, the oxidant is selected from cerium ammonium nitrate and / or cerium ammonium sulfate; Preferably, in step (2), the reaction temperature of the acetal reaction is 25-110°C and the reaction time is 5-24 hours; Preferably, the amount of catalyst added is 1% to 10% of 2 moles of the compound; The molar ratio of compound 2 to neopentyl glycol is 1:(5-12); Preferably, the catalyst is selected from p-toluenesulfonic acid and / or mesitylenesulfonic acid; Preferably, in step (3), the reaction temperature is -100℃ to 100℃ and the reaction time is 5 to 12 hours; Preferably, the molar ratio of compound 3 to compound Ar1 is 1:(4-10); Preferably, the molar ratio of compound Ar1 to n-butyllithium is 1:(1-3), and the molar ratio of stannous chloride to compound 3 is 1:(4-10).

7. A receptor material, characterized in that, The receptor material comprises, in any proportion, a nitrogen-containing fused-ring organic semiconductor compound with aromatic ring-substituted side chains as described in any one of claims 1 to 4.

8. A semiconductor material, characterized in that, The semiconductor material comprises the receptor material of claim 7.

9. A membrane material comprising a photoactive layer, characterized in that, The photoactive layer comprises the semiconductor material of claim 8.

10. An organic optoelectronic device, characterized in that, The organic optoelectronic device comprises the film material of claim 9, and the organic optoelectronic device is selected from organic solar cells, organic field-effect transistors, or photodetectors.

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