Dimer type acceptor material as well as preparation method and application thereof

Abstract

The invention provides a dimer acceptor material as well as a preparation method and application thereof. The structural general formula of the dimer type acceptor material is (I), and the dimer type acceptor material is constructed by taking a rigid unit with a pi conjugated structure as a bridging unit. The acceptor material has a relatively high glass transition temperature and a relatively low diffusion coefficient. The material is used in a photoelectric functional device, can stabilize the film morphology of an active layer, and finally can effectively improve the stability of the device, for example, as an active layer acceptor material of an organic solar cell, can promote commercial application of the organic solar cell.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic photoelectric materials, and specifically relates to a type of dimer type receptor material, a preparation method thereof, and an application thereof in the preparation of photoelectric functional devices such as organic solar cells. Background Art

[0002] As environmental pollution and energy crisis become increasingly serious, the search and development of renewable energy has become an important issue in the development of human society. Among many renewable energy sources (such as solar energy, wind energy, tidal energy, geothermal energy, etc.), solar energy has attracted extensive attention from industry and academia due to its advantages of being pollution-free, widely available, and inexhaustible, and has made great progress.

[0003] Organic Solar Cells (OSCs) are currently the hot third-generation photovoltaic technology. They have attracted widespread attention due to their advantages such as wide source of active layers, light weight, flexible preparation, strong processability and simple manufacturing process (roll-to-roll, printing, spin coating, spray coating, etc.). Currently, organic solar cells have entered a rapid development stage, and their power conversion efficiency (PCE) has exceeded 20%, with broad application prospects. However, their stability issues have become a bottleneck for commercial applications.

[0004] Dimer receptor materials have become strong competitors for small molecule and polymer receptors due to their advantages such as clear structure, good batch reproducibility, good film-forming property, low diffusion coefficient and excellent stability. However, most of the current dimer materials use structures such as thiophene, ethylene, acetylene, thiophene-ethylene-thiophene, thiophene-alkyl chain-thiophene as bridging units, and their glass transition temperatures are all lower than 150°C. The low glass transition temperature and high diffusion coefficient make the molecules more prone to excessive aggregation under thermal stress, which is not conducive to the morphological stability of the active layer and the long service life of the device. Summary of the invention

[0005] The purpose of the present invention is to provide a type of dimer receptor material and its preparation method and application, the material has a high glass transition temperature, and can be used in optoelectronic functional devices to improve the stability of the device. The above purpose can be achieved through the implementation of the following technical solutions:

[0006] The present invention provides a type of dimer receptor material, the general structural formula of the receptor material is (I):

[0007]

[0008] Wherein, in (I), Ar1 and Ar2 both represent rigid units with a π-conjugated structure; X and Y are the same or different hydrogen atoms, F, Cl or Br; and Z is a hydrogen atom, F, Cl or Br.

[0009] Optionally, the Ar1 structural formula is one of (II):

[0010]

[0011] Among them, in (II), R1 and R2 are straight-chain or branched alkyl groups having 10-25 carbon atoms; R3 is a straight-chain or branched alkyl group having 6-10 carbon atoms; R4 is methyl, trifluoromethyl or methoxy; and X is a hydrogen atom, F, Cl or Br.

[0012] Optionally, the Ar2 structural formula is one of (III):

[0013]

[0014] In (III), R is a straight-chain alkyl group.

[0015] Optionally, the glass transition temperature of the receptor material is ≥ 180°C.

[0016] Optionally, the synthetic reaction equation of the receptor material is (IV):

[0017]

[0018] The present invention provides a method for preparing a dimer receptor material, the preparation method comprising the following steps:

[0019] (1) dissolving a dialdehyde-substituted Ar1 compound (a) and a Br-substituted indone compound (b) in an organic solvent at a molar ratio of 1:0.8-1.2, and adding acetic anhydride and boron trifluoride etherate to react for 30-90 minutes. After the reaction is completed, the organic solvent is dried and separated by column chromatography to obtain a unilateral precursor compound (c);

[0020] (2) dissolving the unilateral precursor compound (c) prepared in step (1) and the Ar2 compound (d) substituted with bistrimethyltin in a molar ratio of 2-2.5:1 in an organic solvent, adding a catalyst, a ligand and cuprous iodide, reacting at 100-150° C. for 12-36 hours under an inert gas atmosphere, and after the reaction is completed, drying the organic solvent, and separating by column chromatography to obtain a dialdehyde precursor compound (e);

[0021] (3) The dialdehyde precursor compound (e) prepared in step (2) and the indone compound (f) are dissolved in an organic solvent at a molar ratio of 1:2-4, acetic anhydride and boron trifluoride etherate are added to react for 30-600 minutes. After the reaction is completed, the organic solvent is dried and separated by column chromatography to obtain a dimer receptor material (g).

[0022] Optionally, the organic solvent is chloroform, toluene, chlorobenzene or tetrahydrofuran; the catalyst is Pd(PPh3)4, Pd2(dba)3 or Pd(PPh3)2Cl2; and the ligand is P(o-tol)3 or P(t-Bu)3.

[0023] The invention provides an application of a dimer type receptor material in the preparation of optoelectronic functional devices.

[0024] Optionally, the optoelectronic functional device is an organic solar cell, wherein the dimer type acceptor material is used as an active layer acceptor material and is mixed with a donor material to prepare a photoactive layer of the organic solar cell.

[0025] Optionally, the photoactive layer has a thickness of 80-120 nm.

[0026] Compared with the prior art, the present invention has the following beneficial effects: the dimer receptor material provided by the present invention is constructed with rigid conjugated groups as bridging units, and the material has a higher glass transition temperature and a lower diffusion coefficient. The material can be used in optoelectronic functional devices to improve the stability of the device.

[0027] In a preferred embodiment, the dimer receptor material constructed by the present invention selects a quinoxaline unit with weak electron-withdrawing ability as the central core, and adopts a bridging unit with a large planar rigid structure, indacene and dithiophene, so that the LUMO energy level of the material itself is shifted upward and the glass transition temperature is increased; the material is used in optoelectronic functional devices, such as for preparing the active layer of solar cells, and high opening voltage and high stability OSCs can be obtained. Due to the introduction of large planar conjugated units, the protected molecules all obtain greatly improved glass transition temperatures (not less than 180°C) and reduce the kinetic process of molecular diffusion. The material is used as an organic solar cell active layer receptor material, thereby forming a stable active layer morphology, and ultimately achieving effective improvement in device stability, which is of great significance for the commercial application of organic solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Schematic diagram of the layer structure of an organic solar cell device according to an embodiment of the present invention.

[0029] Figure 2 It is the chemical structural formula of the donor material PM6 in the active layer of the organic solar cell device according to one embodiment of the present invention.

[0030] Figure 3 is the chemical structural formula of PDINN, an electron transport layer material in an organic solar cell device according to an embodiment of the present invention.

[0031] Figure 4 is the chemical structural formula of the hole transport layer material 2PACz in the organic solar cell device according to one embodiment of the present invention.

[0032] Figure 5 It is the general structural formula of the dimer type receptor material provided by the present invention.

[0033] Figure 6 It is a chemical reaction circuit diagram for preparing a dimer type receptor material in one embodiment of the present invention. DETAILED DESCRIPTION

[0034] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] The present invention provides a type of dimer receptor material, which is composed of a bridging unit and two small molecule receptors, and its general structural formula is shown in (I):

[0036]

[0037] Wherein, in (I), Ar1 and Ar2 both represent rigid units with a π-conjugated structure; X and Y are the same or different hydrogen atoms, F, Cl or Br; and Z is a hydrogen atom, F, Cl or Br.

[0038] Furthermore, the Ar1 structural formula is one of (II):

[0039]

[0040] Among them, in (II), R1 and R2 are straight-chain or branched alkyl groups having 10-25 carbon atoms; R3 is a straight-chain or branched alkyl group having 6-10 carbon atoms; R4 is methyl, trifluoromethyl or methoxy; and X is a hydrogen atom, F, Cl or Br.

[0041] Furthermore, the Ar2 structural formula is one of (III):

[0042]

[0043] In (III), R is a straight-chain alkyl group.

[0044] The present invention provides a method for preparing a dimer receptor material, which is prepared by performing three reactions using a dialdehyde-substituted Ar1 compound (a), a Br-substituted indone compound (b), a bistrimethyltin-substituted Ar2 compound (d), and an indone compound (f) as reactants. The organic solvent used in the reaction process can be chloroform, toluene, chlorobenzene or tetrahydrofuran.

[0045] refer to Figure 6 As shown, the following steps are included:

[0046] (1) A dialdehyde-substituted Ar1 compound (a) and a Br-substituted indone compound (b) are dissolved in an organic solvent at a molar ratio of 1:0.8-1.2, and acetic anhydride and boron trifluoride etherate are added to react for 30-90 minutes. After the reaction is completed, the organic solvent is dried and separated by column chromatography to obtain a unilateral precursor compound (c).

[0047] (2) The unilateral precursor compound (c) prepared in step (1) and the Ar2 compound (d) substituted with ditrimethyltin are dissolved in an organic solvent at a molar ratio of 2-2.5:1, and a catalyst, a ligand and cuprous iodide are added, and the reaction is carried out at 100-150° C. for 12-36 hours under an inert gas atmosphere. After the reaction is completed, the organic solvent is dried and separated by column chromatography to obtain a dialdehyde precursor compound (e). The catalyst may be Pd(PPh3)4, Pd2(dba)3 or Pd(PPh3)2Cl2. The ligand may be P(o-tol)3 or P(t-Bu)3.

[0048] (3) The dialdehyde precursor compound (e) prepared in step (2) and the indone compound (f) are dissolved in an organic solvent at a molar ratio of 1:2-4, acetic anhydride and boron trifluoride etherate are added to react for 30-600 minutes. After the reaction is completed, the organic solvent is dried and separated by column chromatography to obtain a dimer receptor material (g).

[0049] The present invention also provides an application of the dimer type receptor material in the preparation of optoelectronic functional devices, for example, in organic solar cell devices. Figure 1 The structure of an organic solar cell device in one embodiment of the present invention is schematically shown. Figure 1 As shown, the layer structure of the organic solar cell device includes: a substrate layer 1, a hole transport layer 2, an active layer 3, an electron transport layer 4 and an electrode 5. The substrate layer 1 can be an ITO substrate. The hole transport layer 2 can be PEDOT:PSS, 2PACz (structure formula as shown in FIG. Figure 4) or ZnO, and its thickness is 20-40nm. The active layer 3 can be a donor material PM6 (structural formula as Figure 2 ) and any dimer type receptor material of the present invention, the thickness of which is 80-120 nm. The electron transport layer 4 can be MoO3 or PDINN (structural formula: Figure 3 ), with a thickness of 5-10 nm. The electrode 5 may be an Al or Ag electrode, with a thickness of 80-100 nm. By using the dimer type acceptor material of the present invention to prepare the active layer in the organic solar cell, OSCs with high opening voltage and high stability can be obtained.

[0050] The technical solution of the present invention is described more clearly and in detail below in conjunction with specific embodiments:

[0051] Example 1: Synthesis of dimeric receptor material DQ1

[0052]

[0053] In the first step, the dialdehyde terminal precursor SMA1 (400 mg, 0.34 mmol), 5-bromocyanoindanone (96 mg, 0.35 mmol) and 50 mL tetrahydrofuran were added to the reaction bottle, and 0.5 mL acetic anhydride and 0.5 mL boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 35 minutes. After the reaction was completed, the solvent was dried, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4:1) to obtain 253 mg of the unilateral precursor compound with a yield of 54%.

[0054] In the second step, a unilateral precursor compound (205 mg, 0.15 mmol), a bridging unit B1 (70 mg, 0.07 mmol), Pd(PPh3)4 (12 mg, 0.01 mmol), and 45 mL of toluene were added to a two-necked bottle, and the mixture was refluxed for 24 h under argon protection. After the reaction, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1), and 130 mg of a dimeric receptor material dialdehyde terminal precursor compound was obtained with a yield of 59%.

[0055] In the third step, a dimeric receptor material dialdehyde terminal precursor compound (130 mg, 0.04 mmol), difluorodicyanoindanone (21 mg, 0.09 mmol) and 22 mL of toluene were added to the reaction bottle, and 0.2 mL of acetic anhydride and 0.3 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 90 min. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to obtain a dimeric receptor material DQ1 (131 mg, yield 89%).

[0056] Example 2: Synthesis of dimer receptor material DQ2

[0057]

[0058] In the first step, the dialdehyde terminal precursor SMA2 (400 mg, 0.35 mmol), 5-bromocyanoindanone (96 mg, 0.35 mmol) and 50 mL toluene were added to the reaction bottle, and 0.5 mL acetic anhydride and 0.5 mL boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 35 minutes. After the reaction was completed, the solvent was dried, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4:1) to obtain 253 mg of the unilateral precursor compound with a yield of 55%.

[0059] In the second step, a unilateral precursor compound (206 mg, 0.16 mmol), a bridging unit B1 (70 mg, 0.07 mmol), Pd(PPh3)4 (16 mg, 0.01 mmol), and 45 mL of toluene were added to a two-necked bottle, and the mixture was refluxed for 24 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1), and 125 mg of a dimeric receptor material dialdehyde terminal precursor compound was obtained with a yield of 56%.

[0060] In the third step, the dimeric receptor material dialdehyde terminal precursor compound (76 mg, 0.02 mmol), difluorobiscyanoindanone (14 mg, 0.06 mmol) and 12 mL of toluene were added to the reaction bottle, and 0.2 mL of acetic anhydride and 0.3 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 90 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to obtain the dimeric receptor material DQ2 (71 mg, yield 83%).

[0061] Example 3: Synthesis of dimeric receptor material DQ3

[0062]

[0063] In the first step, the dialdehyde terminal precursor SMA3 (500 mg, 0.38 mmol), 5-bromocyanoindanone (123 mg, 0.45 mmol) and 50 mL of chloroform were added to the reaction bottle, and 0.5 mL of acetic anhydride and 0.5 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 35 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4:1) to obtain 350 mg of the unilateral precursor compound with a yield of 60%.

[0064] In the second step, a unilateral precursor compound (307 mg, 0.20 mmol), a bridging unit B1 (104 mg, 0.10 mmol), Pd(PPh3)2Cl2 (7 mg, 0.01 mmol), and 35 mL of toluene were added to a two-necked bottle, and the mixture was refluxed for 24 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1), and 219 mg of a dimeric receptor material dialdehyde terminal precursor compound was obtained with a yield of 61%.

[0065] In the third step, a dialdehyde terminal precursor compound (200 mg, 0.06 mmol) of a dimer type receptor material was added to the reaction bottle, 2-(2-chloro-6-oxo-5,6-dihydro-4H-cyclopentadien[b]thiophene-4-ylidene)malononitrile (21 mg, 0.09 mmol) and 12 mL of toluene were added, and 0.3 mL of acetic anhydride and 0.3 mL of boron trifluoride ether were added dropwise under argon protection at room temperature, and the reaction was carried out for 65 min. After the reaction was completed, the solvent was dried by spin drying, the crude product was precipitated in methanol, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to obtain a dimer type receptor material DQ3 (210 mg, yield 93%).

[0066] Example 4: Synthesis of dimeric receptor material DQ4

[0067]

[0068] In the first step, the dialdehyde terminal precursor SMA4 (300 mg, 0.24 mol), 5-bromo-1,3-indandione (59 mg, 0.26 mol) and 50 mL tetrahydrofuran were added to the reaction bottle, and 0.3 mL acetic anhydride and 0.3 mL boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 30 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4:1) to obtain 196 mg of the unilateral precursor compound with a yield of 56%.

[0069] In the second step, a unilateral precursor compound (190 mg, 0.13 mmol), a bridging unit B1 (62 mg, 0.06 mmol), Pd(PPh3)4 (19 mg, 0.01 mmol), and 45 mL of toluene were added to a two-necked bottle, and the mixture was refluxed for 24 h under argon protection. After the reaction, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1), and 142 mg of a dimeric receptor material dialdehyde terminal precursor compound was obtained with a yield of 72%.

[0070] In the third step, a dimeric receptor material dialdehyde terminal precursor compound (140 mg, 0.04 mmol), 5,6-dichloro-1,3-indanedione (19 mg, 0.09 mmol) and 12 mL of toluene were added to the reaction bottle, and 0.2 mL of acetic anhydride and 0.4 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 180 min. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to obtain a dimeric receptor material DQ4 (149 mg, yield 95%).

[0071] Example 5: Synthesis of dimeric receptor material DQ5

[0072]

[0073] In the first step, the dialdehyde terminal precursor SMA5 (453 mg, 0.27 mmol), 6-bromocyanoindanone (76 mg, 0.28 mmol) and 40 mL of chloroform were added to the reaction bottle, and 0.3 mL of acetic anhydride and 0.5 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 35 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4:1) to obtain 340 mg of the unilateral precursor compound with a yield of 68%.

[0074] In the second step, a unilateral precursor compound (335 mg, 0.18 mmol), a bridging unit B1 (83 mg, 0.08 mmol), Pd2(dba)3 (9 mg, 0.01 mmol), P(o-tol)3 (20 mg, 0.05 mmol), CuI (9 mg, 0.05 mmol) and 45 mL of toluene were added to a two-necked bottle and refluxed for 18 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1) to obtain 276 mg of a dimeric receptor material dialdehyde terminal precursor compound with a yield of 82%.

[0075] In the third step, a dimeric receptor material dialdehyde terminal precursor compound (164 mg, 0.04 mmol), diiodobiscyanoindanone (45 mg, 0.10 mmol) and 16 mL toluene were added to the reaction bottle, and 0.5 mL acetic anhydride and 1.0 mL boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 45 min. After the reaction was completed, the solvent was dried, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to obtain a dimeric receptor material DQ5 (180 mg, yield 91%).

[0076] Example 6: Synthesis of dimeric receptor material DQ6

[0077]

[0078] In the first step, the dialdehyde terminal precursor SMA6 (462 mg, 0.30 mmol), 5-bromocyanoindanone (87 mg, 0.32 mmol) and 43 mL of chloroform were added to the reaction bottle, and 0.4 mL of acetic anhydride and 0.3 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 40 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4:1) to obtain 325 mg of a unilateral precursor compound with a yield of 60%.

[0079] In the second step, a unilateral precursor compound (323 mg, 0.18 mmol), a bridging unit B2 (99 mg, 0.08 mmol), Pd2(dba)3 (8 mg, 0.01 mmol), P(o-tol)3 (15 mg, 0.05 mmol) and 45 mL of toluene were added to a two-necked bottle and refluxed for 18 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1) to obtain 268 mg of a dimeric receptor material dialdehyde terminal precursor compound with a yield of 75%.

[0080] In the third step, a dimeric receptor material dialdehyde terminal precursor compound (260 mg, 0.06 mmol), difluorobiscyanoindanone (28 mg, 0.11 mmol) and 22 mL of toluene were added to the reaction bottle, and 0.6 mL of acetic anhydride and 1.0 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 75 min. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to obtain a dimeric receptor material DQ6 (268 mg, yield 94%).

[0081] Example 7: Synthesis of dimeric receptor material DQ7

[0082]

[0083] In the first step, the dialdehyde terminal precursor SMA7 (527 mg, 0.31 mmol), 5-bromocyanoindanone (87 mg, 0.32 mmol) and 40 mL of chloroform were added to the reaction bottle, and 0.4 mL of acetic anhydride and 0.5 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 45 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4:1) to obtain 280 mg of the unilateral precursor compound with a yield of 48%.

[0084] In the second step, a unilateral precursor compound (250 mg, 0.13 mmol), a bridging unit B1 (60 mg, 0.06 mmol), Pd2(dba)3 (6 mg, 0.01 mmol), P(o-tol)3 (12 mg, 0.04 mmol) and 30 mL of toluene were added to a two-necked bottle and refluxed for 18 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1) to obtain 186 mg of a dimeric receptor material dialdehyde terminal precursor compound with a yield of 74%.

[0085] In the third step, a dimeric receptor material dialdehyde terminal precursor compound (170 mg, 0.04 mmol), 5,6-dichloro-1,3-indanedione (24 mg, 0.11 mmol) and 18 mL of toluene were added to the reaction bottle, and 0.7 mL of acetic anhydride and 1.4 mL of boron trifluoride ether were added dropwise under argon protection at room temperature for 75 min. After the reaction, the solvent was dried, the crude product was precipitated in methanol, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: chloroform = 4:1) to obtain a dimeric receptor material DQ7 (176 mg, yield 95%).

[0086] Example 8: Synthesis of dimeric receptor material DQ8

[0087]

[0088] In the first step, the dialdehyde terminal precursor SMA8 (500 mg, 0.34 mmol), 5-bromocyanoindanone (98 mg, 0.36 mmol) and 50 mL of chloroform were added to the reaction bottle, and 0.4 mL of acetic anhydride and 0.6 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 35 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 5:1) to obtain 320 mg of the unilateral precursor compound with a yield of 55%.

[0089] In the second step, a unilateral precursor compound (224 mg, 0.13 mmol), a bridging unit B3 (67 mg, 0.05 mmol), Pd2(dba)3 (4 mg, 0.01 mmol), P(o-tol)3 (7 mg, 0.03 mmol) and 40 mL of toluene were added to a two-necked bottle and refluxed for 18 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 3:1) to obtain 170 mg of a dimeric receptor material dialdehyde terminal precursor compound with a yield of 78%.

[0090] In the third step, a dimeric receptor material dialdehyde terminal precursor compound (150 mg, 0.03 mmol), difluorodicyanoindanone (25 mg, 0.12 mmol) and 25 mL toluene were added to the reaction bottle, and 0.7 mL acetic anhydride and 1.3 mL boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 60 min. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:3) to obtain a dimeric receptor material DQ8 (152 mg, yield 92%).

[0091] Example 9: Synthesis of dimeric receptor material DQ9

[0092]

[0093] In the first step, the dialdehyde terminal precursor SMA8 (589 mg, 0.40 mmol), 2-(2-bromo-6-oxo-5,6-dihydro-4H-cyclopentadien[b]thiophene-4-ylidene)malononitrile (112 mg, 0.40 mmol) and 50 mL of toluene were added to the reaction bottle, and 0.6 mL of acetic anhydride and 0.7 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 50 minutes. After the reaction was completed, the solvent was dried, the crude product was precipitated in methanol, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 5:1) to obtain 424 mg of a unilateral precursor compound with a yield of 61%.

[0094] In the second step, a unilateral precursor compound (260 mg, 0.15 mmol), a bridging unit B3 (81 mg, 0.06 mmol), Pd2(dba)3 (9 mg, 0.01 mmol), P(o-tol)3 (18 mg, 0.06 mmol) and 40 mL of toluene were added to a two-necked bottle and refluxed for 21 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: chloroform = 4:1) to obtain 180 mg of a dimeric receptor material dialdehyde terminal precursor compound with a yield of 69%.

[0095] In the third step, a dimeric receptor material dialdehyde terminal precursor compound (130 mg, 0.03 mmol), difluorodicyanoindanone (21 mg, 0.09 mmol) and 25 mL of toluene were added to the reaction bottle, and 0.7 mL of acetic anhydride and 1.3 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 60 min. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:3) to obtain a dimeric receptor material DQ9 (126 mg, yield 88%).

[0096] Example 10: Synthesis of dimeric receptor material DQ10

[0097]

[0098] In the first step, the dialdehyde terminal precursor SMA9 (630 mg, 0.36 mmol), 5-bromocyanoindanone (98 mg, 0.36 mmol) and 50 mL toluene were added to the reaction bottle, and 0.4 mL acetic anhydride and 0.5 mL boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 50 minutes. After the reaction was completed, the solvent was dried by spin drying, and the crude product was precipitated in methanol. The obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 5:1) to obtain 410 mg of the unilateral precursor compound with a yield of 57%.

[0099] In the second step, a unilateral precursor compound (220 mg, 0.11 mmol), a bridging unit B4 (47 mg, 0.05 mmol), Pd(PPh3)2Cl2 (8 mg, 0.01 mmol) and 25 mL of toluene were added to a two-necked bottle and refluxed for 28 h under argon protection. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was dried to obtain a crude product. The obtained crude product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 1:1) to obtain 180 mg of a dimeric receptor material dialdehyde terminal precursor compound with a yield of 87%.

[0100] In the third step, the dimeric receptor material dialdehyde terminal precursor compound (164 mg, 0.04 mmol), 5,6-dichloro-1,3-indanedione (23 mg, 0.10 mmol) and 18 mL of toluene were added to the reaction bottle, and 0.5 mL of acetic anhydride and 1.0 mL of boron trifluoride ether were added dropwise at room temperature under argon protection, and the reaction was carried out for 75 min. After the reaction, the solvent was dried by spin drying, the crude product was precipitated in methanol, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: chloroform = 3:1) to obtain the dimeric receptor material DQ10 (173 mg, yield 97%).

[0101] Example 11: Glass transition temperature test of dimer receptor material

[0102] The glass transition temperature test of the dimer receptor materials obtained in Examples 1 to 10 is performed, and the specific process is as follows:

[0103] The solution (chloroform solution of DQ1 to DQ10, solution concentration = 10 mg / mL) was spin-coated on a quartz glass substrate to prepare a thin film, and the glass transition temperature of DQ1 to DQ10 was obtained by calculating the red shift deviation metric measured by the UV-visible absorption spectrum of the temperature change, as shown in Table 1 below.

[0104] Table 1 Glass transition temperature of DQ1 to DQ10

[0105] Material Glass transition temperature(℃) DQ1 189 DQ2 207 DQ3 196 DQ4 189 DQ5 180 DQ6 201 DQ7 199 DQ8 212 DQ9 205 DQ10 182

[0106] It can be seen from Table 1 that the glass transition temperatures of the dimer receptor materials DQ1 to DQ10 prepared in the above examples are increased and are not lower than 180°C.

[0107] Example 12: Device preparation of organic solar cells based on dimer acceptor materials

[0108] The dimer acceptor material obtained in Examples 1 to 10 was used as an active layer acceptor material to prepare an organic solar cell device. The specific preparation process is as follows:

[0109] The active layer solution (donor material and acceptor material in the same ratio, such as PM6:DQ1 = 1:1, solution concentration = 14 mg / mL) was spin-coated on the ITO glass substrate modified with PEDOT:PSS to prepare the photoactive layer. The active layer was thermally annealed (100 °C / 10 min) and then spin-coated with PDINN (concentration: 1.0 mg mL -1 The cathode was prepared by evaporating Ag.

[0110] Photovoltaic device performance: in white light 1.5G (100mW cm-2 ) irradiation, device performance and T 90 The lifespan (time to maintain 90% of the initial efficiency) is shown in Table 2 below, where V oc represents the open circuit voltage, J sc represents short-circuit current, FF represents fill factor, and PCE represents photoelectric conversion efficiency.

[0111] Table 2 Photovoltaic device performance

[0112] Active layer <![CDATA[V oc (V)]]> <![CDATA[J sc (V)]]> FF(%) PCE(%) <![CDATA[T 90 (h)]]> PM6:DQ1 1.06 21.20 72 16.18 1300 PM6:DQ2 1.02 22.31 71 16.16 1696 PM6:DQ3 1.04 22.15 73 16.82 2040 PM6:DQ4 1.08 20.12 70 15.21 1308 PM6:DQ5 0.99 21.98 72 15.66 1726 PM6:DQ6 1.02 22.03 71 15.95 1496 PM6:DQ7 1.08 21.99 72 17.10 2108 PM6:DQ8 1.10 21.86 71 17.07 1820 PM6:DQ9 1.09 22.01 69 16.55 1592 PM6:DQ10 1.11 22.98 72 18.36 1600

[0113] It can be seen from the above table that the organic solar cell device prepared by using the dimer type acceptor material prepared in the above embodiment as the active layer acceptor material has an open circuit voltage of ≥0.99V, T 90 The photoelectric conversion efficiency reaches 1300h, especially exceeds 2000h, and is greater than 15%.

[0114] The description of the present invention is given for the purpose of illustration and description, and is not intended to be exhaustive or to limit the invention to the disclosed form. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments are selected and described in order to better illustrate the principles and practical applications of the present invention and to enable those of ordinary skill in the art to understand the present invention and thereby design various embodiments with various modifications suitable for particular uses.

Claims

1. A type of dimer receptor material, characterized in that: The general structural formula of the receptor material is (I)： Wherein, in (I), Ar1 and Ar2 both represent rigid units with a π-conjugated structure; X and Y are the same or different hydrogen atoms, F, Cl or Br; and Z is a hydrogen atom, F, Cl or Br.

2. A dimer receptor material according to claim 1, characterized in that: The Ar1 structural formula is one of (II): Among them, in (II), R1 and R2 are straight-chain or branched alkyl groups having 10-25 carbon atoms; R3 is a straight-chain or branched alkyl group having 6-10 carbon atoms; R4 is methyl, trifluoromethyl or methoxy; and X is a hydrogen atom, F, Cl or Br.

3. A dimer type receptor material according to claim 1, characterized in that: The Ar2 structural formula is one of (III): In (III), R is a straight-chain alkyl group.

4. The dimer type receptor material according to claim 1, characterized in that: The glass transition temperature of the receptor material is ≥180°C.

5. The dimer receptor material according to claim 1, characterized in that: The synthetic reaction equation of the receptor material is (IV):

6. A method for preparing a dimer receptor material according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: (1) dissolving a dialdehyde-substituted Ar1 compound (a) and a Br-substituted indone compound (b) in an organic solvent at a molar ratio of 1:0.8-1.2, and adding acetic anhydride and boron trifluoride etherate to react for 30-90 minutes. After the reaction is completed, the organic solvent is dried and separated by column chromatography to obtain a unilateral precursor compound (c); (2) dissolving the unilateral precursor compound (c) prepared in step (1) and the Ar2 compound (d) substituted with bistrimethyltin in a molar ratio of 2-2.5:1 in an organic solvent, adding a catalyst, a ligand and cuprous iodide, reacting at 100-150° C. for 12-36 hours under an inert gas atmosphere, and after the reaction is completed, drying the organic solvent, and separating by column chromatography to obtain a dialdehyde precursor compound (e); (3) The dialdehyde precursor compound (e) prepared in step (2) and the indone compound (f) are dissolved in an organic solvent at a molar ratio of 1:2-4, acetic anhydride and boron trifluoride etherate are added to react for 30-600 minutes. After the reaction is completed, the organic solvent is dried and separated by column chromatography to obtain a dimer receptor material (g).

7. The preparation method according to claim 6, characterized in that: The organic solvent is chloroform, toluene, chlorobenzene or tetrahydrofuran; The catalyst is Pd(PPh3)4, Pd2(dba)3 or Pd(PPh3)2Cl2; The ligand is P(o-tol)3 or P(t-Bu)3.

8. Use of a dimer receptor material as claimed in any one of claims 1 to 5 in the preparation of optoelectronic functional devices.

9. The use according to claim 8, characterized in that: The optoelectronic functional device is an organic solar cell, wherein the dimer type acceptor material is used as an active layer acceptor material and is mixed with a donor material to prepare a photoactive layer of the organic solar cell.

10. The use according to claim 9, characterized in that: The photoactive layer has a thickness of 80-120 nm.

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