Non-condensed ring small molecule material and application thereof in organic solar cell

Abstract

The invention relates to the field of organic solar cell materials, and discloses a non-condensed ring small molecule material and application thereof in an organic solar cell, the non-condensed ring small molecule material has a structure as shown in a general formula (I), the conformation of a non-condensed ring receptor is locked by introducing an S-N, S-O non-covalent bond, so that the rotation of a C-C single bond is effectively limited, and the structure of the non-condensed ring small molecule material is improved. Ordered molecule accumulation and efficient electron transmission are achieved, the device performance is improved, meanwhile, the synthesis cost of the material is reduced, and when the material is applied to an organic solar cell device, high photoelectric conversion efficiency is achieved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of organic solar cell materials, and in particular to a non-condensed ring small molecule material and an application thereof in an organic solar cell. Background Art

[0002] Organic solar cells (OPV) have the advantages of light weight, translucency, flexibility, designability, easy large-area printing and preparation, and on-demand regulation. They have become a new generation of photovoltaic technology with broad application prospects and can be widely used in wearable devices, smart Internet of Things, smart homes, smart agriculture, building photovoltaics, automotive photovoltaics and other fields.

[0003] With the continuous development and improvement of molecular design strategies, especially the successful development of Y-type condensed ring electron acceptors, such as the development of structures such as Y6, L8-BO, and BTP-eC9, OPV device performance has made significant progress in the past few years, and the photoelectric conversion efficiency (PCE) has approached 20%. However, the Y-type condensed ring acceptor contains a large condensed ring core, the synthesis route is long and the material cost is high, which greatly limits the industrial application of organic photovoltaics.

[0004] In recent years, the development of non-condensed ring small molecule receptor materials has received more and more attention. Compared with condensed ring small molecule receptors, non-condensed ring small molecule receptors have the advantages of simple structure and easy synthesis, which greatly reduces the complexity of material synthesis and the production cost of materials. However, compared with condensed ring small molecule receptors, non-condensed ring small molecule receptor materials can rotate through the CC single bond, causing the molecule to produce conformational isomers, resulting in a distorted configuration and destroying the coplanarity of the molecular skeleton, thereby affecting the molecular aggregation morphology and reducing the photoelectric performance of the material and the photoelectric conversion efficiency of the device.

[0005] In order to solve the problem of poor planarity of non-condensed ring small molecule receptors, CN113880829A proposes to use the conformational locking effect of large steric hindrance groups to limit the free rotation of the conjugated skeleton, thereby improving the planarity of the skeleton structure; CN115650971A discloses a non-condensed ring small molecule receptor with bithiazole as the central unit. The small molecule receptor with bithiazole as the central unit introduces a large steric hindrance group phenyl aromatic ring at the side chain position of the central thiophene unit, so that the non-condensed ring small molecule receptor can form a stable planar structure, enhance the delocalization of π electrons, and the transfer within and between molecules; and further through the van der Waals force between molecules, it is conducive to the formation of a conjugated structure, thereby obtaining a non-condensed ring electron receptor with a higher electron transfer effect.

[0006] However, such compounds are difficult to synthesize due to the large steric hindrance of the core structure. Therefore, it is necessary to develop new non-condensed ring small molecule receptor materials to solve the shortcomings of the existing technology. Summary of the invention

[0007] Based on the problems existing in the above-mentioned prior art, the present invention provides a new type of non-condensed ring small molecule material, which locks the conformation of the non-condensed ring receptor by introducing S-N and S--O non-covalent bonds, thereby effectively restricting the rotation of the CC single bond, achieving orderly molecular stacking and efficient electron transmission, thereby achieving improved device performance while reducing the synthesis cost of the material.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] A non-condensed ring small molecule material having a structure as shown in general formula (I):

[0010]

[0011] in:

[0012] R1, R2, R3, each occurrence, is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -CF3, -NO2, straight-chain alkyl having 1-20 C atoms, branched-chain alkyl having 3-20 C atoms, straight-chain alkoxy having 1-20 C atoms, branched-chain alkoxy having 3-20 C atoms, straight-chain alkylthio having 1-20 C atoms, or branched-chain alkylthio having 3-20 C atoms;

[0013] Each occurrence of R4 is independently selected from a straight chain alkyl group having 1 to 20 C atoms, or a branched chain alkyl group having 3 to 20 C atoms;

[0014] Ar1 and Ar2 are independently selected from unsubstituted or substituted with one or more R * Substituted aromatic radicals having 6-10 carbon atoms, unsubstituted or replaced by one or more R * Substituted heteroaromatic groups having 5 to 10 ring atoms;

[0015] R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF3, -NO2, straight-chain alkyl having 1-10 C atoms, branched-chain alkyl having 3-10 C atoms, straight-chain alkoxy having 1-10 C atoms, branched-chain alkoxy having 3-10 C atoms, straight-chain alkylthio having 1-10 C atoms, or branched-chain alkylthio having 3-10 C atoms.

[0016] The present invention creatively introduces a side chain thiophene group into the core group thiophene-thiophene, and the S atom on the side chain thiophene and the N on the main chain thiazole are conformationally locked through the S---N non-covalent bond, thereby effectively restricting the rotation of the CC single bond; in order to further achieve the orderliness of the molecule, the present invention further introduces alkoxy substitution on the main chain thiophene, and at the same time the S---O non-covalent bond realizes the conformational locking between thiophene and thiazole. The non-condensed ring small molecule material according to the present invention has good molecular stacking and efficient electron transmission, and further when used as a photoactive layer receptor material in an organic solar cell device, a high photoelectric conversion efficiency is achieved.

[0017] In some embodiments, Ar1 and Ar2 are independently selected from the following groups:

[0018]

[0019] Wherein: n1 is independently selected from 0, 1, 2, 3 or 4 at each occurrence; n2 is independently selected from 0, 1, 2, 3, 4, 5 or 6 at each occurrence; n3 is independently selected from 0, 1 or 2 at each occurrence;

[0020] * indicates a fusion site, which is selected from a C atom.

[0021] In some embodiments, Ar1 and Ar2 are independently selected from the following groups:

[0022]

[0023] Wherein: n1 is independently selected from 0, 1, 2, 3 or 4 at each occurrence; n2 is independently selected from 0, 1, 2, 3, 4, 5 or 6 at each occurrence; n3 is independently selected from 0, 1 or 2 at each occurrence;

[0024] * indicates a fusion site, which is selected from a C atom.

[0025] In some embodiments, the non-condensed ring small molecule material is selected from any one of the general formulas (II-1) to (II-4):

[0026]

[0027] In some embodiments, the R * Each occurrence is independently selected from -D (deuterium), -F, -Cl, -Br, -I, -CN, -CF3, -NO2, straight-chain alkyl having 1-6 C atoms, branched-chain alkyl having 3-6 C atoms, straight-chain alkoxy having 1-6 C atoms, branched-chain alkoxy having 3-6 C atoms, straight-chain alkylthio having 1-6 C atoms, or branched-chain alkylthio having 3-16 C atoms.

[0028] In some embodiments, the R* Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF3, -NO2, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, methoxy, or methylthio.

[0029] In some embodiments, in Formula II-1 Selected from any of the following groups:

[0030]

[0031] Wherein: # indicates the connection site.

[0032] In some embodiments, in Formula II-2 Selected from any of the following groups:

[0033]

[0034] In some embodiments, in Formula II-3 Selected from any of the following groups:

[0035]

[0036] In some embodiments, in Formula II-4 Selected from any of the following groups:

[0037]

[0038] In some embodiments, each occurrence of R1 is independently selected from a straight chain alkyl having 1-16 C atoms, a branched chain alkyl having 3-16 C atoms, a straight chain alkoxy having 1-16 C atoms, a branched chain alkoxy having 3-16 C atoms, a straight chain alkylthio having 1-16 C atoms, or a branched chain alkylthio having 3-16 C atoms;

[0039] In some embodiments, each occurrence of R2 and R3 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -CF3, -NO2, a straight chain alkyl group having 1-10 C atoms, a branched chain alkyl group having 3-10 C atoms;

[0040] In some embodiments, each occurrence of R4 is independently selected from a straight chain alkyl group having 4-20 C atoms, or a branched chain alkyl group having 4-20 C atoms.

[0041] In some embodiments, each occurrence of R4 is independently selected from a straight chain alkyl group having 4-10 C atoms, or a branched chain alkyl group having 4-10 C atoms.

[0042] In some embodiments, each occurrence of R2 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, or -CF3.

[0043] In some embodiments, each occurrence of R3 is independently selected from -H, -D, or -F.

[0044] In some embodiments, each occurrence of R2 and R3 is selected from -H.

[0045] In one embodiment, each occurrence of R1 is independently selected from a straight chain alkyl group having 1-10 C atoms, a branched chain alkyl group having 3-10 C atoms; and R2 and R3 are selected from -H.

[0046] In some embodiments, the non-condensed ring small molecule material is selected from the following structures:

[0047]

[0048]

[0049] The present invention further relates to a photoactive layer receptor material, wherein the photoactive layer receptor material is selected from the non-condensed ring small molecule materials described above.

[0050] The present invention also provides a mixture, wherein the mixture comprises a photoactive layer donor material and a photoactive layer acceptor material, wherein the photoactive layer acceptor material is selected from the non-condensed ring small molecule material as described above.

[0051] In some embodiments, the photoactive layer donor material is selected from one or two or more of PBDB-T, PM6, PM7, D18, D18-Cl, PBQx-TCl, PTQ10, and PTQ11, but is not limited thereto, and commonly used donor materials in the art may be included.

[0052] In some embodiments, according to the mixture of the present invention, the mass ratio of the photoactive layer donor material to the photoactive layer acceptor material is 1:1 to 1:1.8; preferably, the mass ratio is 1:1 to 1:1.5; preferably, the mass ratio is 1:1 to 1:1.2.

[0053] The present invention also provides a composition, which comprises the non-condensed ring small molecule material or mixture, and at least one organic solvent.

[0054] In some embodiments, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0055] In some embodiments, according to the composition of the present invention, the concentration of the mixture in the organic solvent is selected from 6-30 mg / mL; further, the concentration of the mixture in the organic solvent is selected from 6-20 mg / mL.

[0056] Furthermore, the composition further comprises an additive, and the additive may be selected from a liquid additive or a solid additive.

[0057] Preferably, the additive is selected from 1,8-diiodooctane (DIO), diphenyl ether (DPE), anthracene, or one or more halogen-substituted phenyl groups; preferably, the one or more halogen-substituted phenyl groups are selected from 1,4-diiodobenzene (DIB), 1,3-dibromo-5-chlorobenzene (DBCl), 3,5-dichlorobromobenzene (DCBB), 1-chloronaphthalene (1-CN), 1,3,5-tribromobenzene (TBB), etc., but are not limited thereto.

[0058] The present invention also provides an organic solar cell device, which comprises at least a cathode, an anode, and a photoactive layer located between the cathode and the anode, wherein the photoactive layer material comprises the non-condensed ring small molecule material or mixture as described above, or is prepared from the above composition.

[0059] The materials used to prepare the electrodes (cathode and anode) can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides, such as ZnO:Al or SnO2:Sb, etc.; and conductive polymers, such as PEDOT:PSS, polypyrrole and polyaniline, etc.; or materials with a multilayer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2 and Al:BaF2:Ba, etc., but are not limited to these.

[0060] The materials used to prepare the photoactive layer may be selected from the mixtures or combinations described above.

[0061] In some embodiments, the thickness of the photoactive layer is 50 to 300 nm; further, the thickness of the photoactive layer is 50 to 150 nm.

[0062] Furthermore, the organic solar cell device further comprises an anode buffer layer, wherein the anode buffer layer is located between the anode and the photoactive layer.

[0063] Furthermore, the anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoOx), vanadium oxide (V2O5), nickel oxide (NiOx), tungsten oxide (WOx, preferably, x is selected from 2 or 3), or self-assembled materials such as 2PACz, MeO-2PACz, etc., but is not limited thereto.

[0064] Furthermore, the organic solar cell device further comprises a cathode buffer layer, wherein the cathode buffer layer is located between the cathode and the photoactive layer.

[0065] Furthermore, the cathode buffer layer material is selected from metal oxides or polymers. The metal oxide may be a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc. The polymer may be PFN-Br, PFN, PDINN, PDINO, PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited thereto.

[0066] It should be noted that, in order to improve the performance of the organic solar cell device, the functional layer may further include other functional layers, including but not limited to a charge blocking layer.

[0067] In some embodiments, the organic solar cell further comprises a substrate. Specifically, the substrate may be disposed on one side of the anode and on a different side from the photoactive layer.

[0068] In some embodiments, the organic solar cell further comprises a substrate. Specifically, the substrate may be disposed on one side of the cathode and on a different side from the photoactive layer.

[0069] Specifically, the substrate can use a substrate with excellent transparency, surface smoothness, ease of operation and water resistance. For example, a glass substrate, a thin film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in a single or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and polyimide (PI), but is not limited thereto, and substrates commonly used for organic solar cells may also be used.

[0070] The organic solar cell device according to the present invention can be applied to wearable devices, smart Internet of Things, smart homes, smart agriculture, building photovoltaics, vehicle-mounted photovoltaics and other fields.

[0071] Compared with the prior art, the present invention has the following beneficial effects:

[0072] (1) The non-condensed ring small molecule in the present invention uses thiophene as the core group, introduces the side chain of the thiophene group, and locks the conformation through the S---N non-covalent bond, thereby effectively restricting the rotation of the CC single bond, thereby improving the orderliness of the molecule; the non-condensed ring small molecule material has good molecular stacking and efficient electron transmission, and further, when used as a photoactive layer acceptor material in an organic solar cell device, a high photoelectric conversion efficiency is achieved.

[0073] (2) The preparation method of the non-condensed ring small molecule in the present invention is simple, the raw materials are cheap and easily available, the synthesis cost is low, and it is convenient for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 Schematic diagram of the structure of an organic solar cell device in a device embodiment of the present invention. DETAILED DESCRIPTION

[0075] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Those skilled in the art can make modifications or equivalent substitutions based on the understanding of the technical scheme of the present invention without departing from the spirit and scope of the technical scheme of the present invention, and all should be included in the protection scope of the present invention.

[0076] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0077] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0078] In the description of the present invention, it should be understood that the terms "upper", "lower", "between layers", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, or are the orientations or positional relationships in which the organic solar cell device is conventionally placed when in use, or are the orientations or positional relationships conventionally understood by those skilled in the art. These are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0079] In the present invention, when the position of the substituent on the group is not fixed, it means that any connectable site in the group can be used as a connecting site. Can be expressed

[0080] In the present invention, organic photovoltaic device, organic solar cell and OPV have the same meaning and can be interchangeable.

[0081] In the present invention, active layer and photoactive layer have the same meaning and can be interchanged.

[0082] In the present invention, "alkyl" may represent a straight chain, branched chain and / or cyclic alkyl group. The number of carbon atoms of a straight chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, 1 to 6, or 1 to 4; the number of carbon atoms of a branched chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4; the number of carbon atoms of a cyclic alkyl group may be 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4. Non-limiting examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; non-limiting examples of branched chain alkyl groups include isopropyl, tert-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, isopentyl, neopentyl, tert-pentyl, and the like.

[0083] The term "alkoxy" refers to a group with the structure "-O-alkyl", i.e., an alkyl group as defined above is connected to another group via an oxygen atom. The straight-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, 1 to 6 or 1 to 4; the branched-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, 3 to 6 or 3 to 4.

[0084] The term "alkylthio" refers to a group having the structure "-S-alkyl", i.e., an alkyl group as defined above connected to another group via a sulfur atom. The straight-chain alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a straight-chain alkyl group, wherein the carbon number of the straight-chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, 1 to 6, or 1 to 4; the branched-chain alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, 3 to 6, or 3 to 4.

[0085] In the present invention, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of quinoline is 10, the number of ring atoms of a thienyl group is 5, and the number of ring atoms of thienothiophene is 8.

[0086] In the process of describing the structural elements of the present invention, the words "including" or "comprising" or "at least one" and the like used in the present invention mean that the device or material appearing before the word covers the devices or materials listed after the word and their equivalents, but does not exclude other devices or materials.

[0087] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0088] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0089] Synthesis Example 1: Synthesis of compound (2), the reaction formula is as follows:

[0090]

[0091] Synthesis of Compound 2-3

[0092] Compound 2-1 (59.5 g, 0.3 mol), 2-2 (165.4 g, 0.33 mol), tetrakistriphenylphosphine palladium (3.5 g, 3 mmol) were added to a 2000 mL three-necked flask, 1000 mL of anhydrous toluene was added, argon was replaced three times, and the temperature was raised to 90 ° C for 12 hours. TLC monitoring of the reaction was completed, the reaction solution was cooled to room temperature, water was added to separate, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried by spin drying and separated by silica gel column chromatography, and the eluent was PE:DCM = 15:1 (volume ratio), and about 70.6 g of compound 2-3 was obtained, with a yield of 71.3%, MS: 329.77.

[0093] Synthesis of Compound 2-6

[0094] Compound 2-4 (29.8 g, 0.1 mol), 2-5 (71.8 g, 0.2 mol), tetrakistriphenylphosphine palladium (2.3 g, 2 mmol) were added to a 1000 mL three-necked flask, 500 mL of anhydrous toluene was added, argon was replaced three times, and the temperature was raised to 110 ° C for 6 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, water was added to separate, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried by spin drying and separated by silica gel column chromatography, and the eluent was PE to obtain about 40.7 g of compound 2-6, with a yield of 76.9%, MS: 528.80.

[0095] Synthesis of Compound 2-8

[0096] Compound 2-6 (37.0 g, 70 mmol) and 450 mL of anhydrous tetrahydrofuran were added to a 1000 mL three-necked flask in sequence. After replacing argon three times, the temperature was cooled to -78 ° C in a liquid nitrogen ethanol bath. N-butyl lithium (2.5 M, 70 mL) was slowly added to the reaction system. After keeping -78 ° C for 1 hour, compound 2-7 (57.0 g, 175 mmol) was slowly added to the reaction system. After half an hour, the ice bath was removed, and the temperature naturally returned to room temperature for 2 hours. The reaction solution was poured into water to quench. Separate the liquid, and the aqueous phase was extracted twice with ethyl acetate. Combine the organic phases, wash with saturated brine, separate the liquids, and dry the organic phase with anhydrous sodium sulfate and filter. The filtrate was mixed with the sample and dried, and separated by vacuum neutral alumina column chromatography, and the eluent was n-hexane to obtain about 47.5 g of compound 2-8, with a yield of 61.3%, MS: 1106.72.

[0097] Synthesis of Compound 2-9

[0098] Compound 2-8 (44.3 g, 40 mmol), 2-3 (28.0 g, 85 mmol), tetrakistriphenylphosphine palladium (1.85 g, 1.6 mmol) were added to a 500 mL three-necked flask, 250 mL of anhydrous toluene was added, argon was replaced three times, and the temperature was raised to 110 ° C for 12 hours. TLC monitored the end of the reaction, the reaction solution was cooled to room temperature, water was added to separate, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried by spin drying and separated by silica gel column chromatography, the eluent was PE:DCM = 15:1 (volume ratio), and about 28.3 g of compound 2-9 was obtained, with a yield of 63.5%, MS: 1115.46.

[0099] Synthesis of Compound 2-10

[0100] Compound 2-9 (22.3 g, 20 mmol) was added to a 500 mL three-necked flask, and 200 mL of anhydrous DMF was added. After replacing argon three times, the mixture was cooled to 0°C in an ice-salt bath. Phosphorus oxychloride (15.3 g, 100 mmol) was weighed and slowly added dropwise to the reaction system. After the addition was completed, the mixture was stirred at 0°C for 1 hour, and then heated to 80°C for 12 hours. The mixture was cooled to room temperature, poured into water for quenching, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate. The excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:DCM=10:1 (volume ratio), to obtain about 18.4 g of compound 2-10, with a yield of 78.6% and MS of 1171.84.

[0101] Synthesis of compound (2):

[0102] Compound 2-10 (2.9 g, 2.5 mmol), compound 2-11 (1.2 g, 5.2 mmol), and 5.0 mL of piperidine were added to a 250 ml three-necked flask, and 100 mL of chloroform was added. After replacing the argon gas three times, the temperature was raised to 60 ° C and the reaction was carried out for 12 hours. Cooled to room temperature, the excess solvent was removed by vacuum distillation. The crude product was washed with 100 mL of methanol and filtered. The filter cake was dissolved in dichloromethane and added to silica gel for column chromatography. The eluent was PE:DCM = 6:1 (volume ratio). About 2.7 g of compound (2) was obtained, with a yield of 68.3%, and MALDI-TOF-MS: 1596.24.

[0103] Synthesis Example 2: Synthesis of Compound (7)

[0104]

[0105] Synthesis of compound 7-3

[0106] Compound 7-1 (42.9 g, 0.2 mol) and 400 mL of anhydrous tetrahydrofuran were added to a 1000 mL three-necked flask in sequence. After replacing argon three times, the temperature was cooled to -78 ° C in a liquid nitrogen ethanol bath. Diisopropylamine lithium (2M, 150 mL) was slowly added to the reaction system. After keeping -78 ° C for 1 hour, compound 7-2 (64.3 g, 0.3 mol) was slowly added to the reaction system. After half an hour, the liquid nitrogen ethanol bath was removed, and the temperature naturally returned to room temperature for 2 hours. The reaction solution was poured into water for quenching. Liquid separation, the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried and separated by vacuum neutral alumina column chromatography, and the eluent was petroleum ether to obtain about 62.4 g of compound 7-3 with a yield of 82.7%. MS: 377.42.

[0107] Synthesis of compound 7-4

[0108] Compound 7-3 (60.3 g, 160 mmol), 2-4 (23.8 g, 80 mol), and tetrakistriphenylphosphine palladium (3.7 g, 3.2 mmol) were added to a 1000 mL three-necked flask, and 500 mL of anhydrous toluene was added. After replacing argon three times, the temperature was raised to 110 ° C and the reaction was carried out for 12 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, separated by adding water, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried by spin drying and separated by silica gel column chromatography. The eluent was PE:DCM = 20:1 (volume ratio), and about 34.6 g of compound 7-4 was obtained, with a yield of 76.5%. MS: 565.03 Synthesis of compound 7-5

[0109] Compound 7-4 (28.2 g, 50 mmol) and 400 mL of anhydrous tetrahydrofuran were added to a 1000 mL three-necked flask in sequence. After replacing argon three times, the temperature was cooled to -78 ° C in a liquid nitrogen ethanol bath. N-butyl lithium (2.5 M, 50 mL) was slowly added to the reaction system. After keeping -78 ° C for 1 hour, compound 2-7 (40.7 g, 175 mmol) was slowly added to the reaction system. After half an hour, the ice bath was removed, and the reaction was naturally warmed to room temperature for 2 hours. The reaction solution was poured into water to quench. Separate the liquid, and the aqueous phase was extracted twice with ethyl acetate. Combine the organic phases, wash with saturated brine, separate the liquids, and dry the organic phase with anhydrous sodium sulfate and filter. The filtrate was mixed with a sample and dried, and separated by vacuum neutral alumina column chromatography, and the eluent was n-hexane, to obtain about 44.3 g of compound 7-5, with a yield of 77.5%. MALDI-TOF-MS: 1143.12.

[0110] Synthesis of compound 7-6

[0111] Compound 7-5 (17.1 g, 15 mmol), 2-3 (21.4 g, 32 mmol), tetrakistriphenylphosphine palladium (1.85 g, 1.6 mmol) were added to a 500 mL three-necked flask, 250 mL of anhydrous toluene was added, argon was replaced three times, and the temperature was raised to 110 ° C for 12 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, water was added to separate, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried by spin drying and separated by silica gel column chromatography, and the eluent was PE:DCM = 10:1 (volume ratio), and about 14.2 g of compound 7-6 was obtained, with a yield of 82.4%. MALDI-TOF-MS: 1151.86.

[0112] Synthesis of compound 7-7

[0113] Compound 7-6 (11.5 g, 10 mmol) was added to a 500 mL three-necked flask, and 200 mL of anhydrous DMF was added. After replacing argon three times, the mixture was cooled to 0°C in an ice-salt bath. Phosphorus oxychloride (7.6 g, 50 mmol) was weighed and slowly added dropwise to the reaction system. After the addition was completed, the mixture was stirred at 0°C for 1 hour, and then heated to 80°C for 12 hours. The mixture was cooled to room temperature, poured into water for quenching, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate. The excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:DCM=15:1 (volume ratio). About 8.9 g of compound 7-7 was obtained, with a yield of 73.6%. MALDI-TOF-MS: 1207.91.

[0114] Synthesis of compound (7):

[0115] Compound 7-7 (3.0 g, 2.5 mmol), compound 2-11 (1.2 g, 5.2 mmol), and 5.0 mL of piperidine were added to a 250 mL three-necked flask, and 100 mL of chloroform was added. After replacing the argon gas three times, the temperature was raised to 60 ° C and the reaction was continued for 12 hours. Cooled to room temperature, the excess solvent was removed by vacuum distillation. The crude product was washed with 100 mL of methanol and filtered. The filter cake was dissolved in dichloromethane and added to silica gel for column chromatography. The eluent was PE:DCM = 15:1 (volume ratio). About 2.6 g of compound (7) was obtained, and the yield was 63.7%. MALDI-TOF-MS: 1632.49.

[0116] Synthesis Example 3: Synthesis of Compound (10)

[0117]

[0118] Synthesis of compound (10):

[0119] Compound 2-10 (2.9 g, 2.5 mmol), compound 10-1 (1.4 g, 5.2 mmol), and 5.0 mL of piperidine were added to a 250 mL three-necked flask, and 100 mL of chloroform was added. After replacing the argon gas three times, the temperature was raised to 60°C and the reaction was continued for 12 hours. The mixture was cooled to room temperature and the excess solvent was removed by distillation under reduced pressure. The crude product was washed with 150 mL of methanol and filtered. The filter cake was dissolved in dichloromethane and added to silica gel for column chromatography. The eluent was PE:DCM=20:1 (volume ratio). About 2.4 g of compound (10) was obtained, with a yield of 58.4%. MALDI-TOF-MS: 1661.88.

[0120] Synthesis Example 4: Synthesis of Compound (17)

[0121]

[0122] Synthesis of compound (17):

[0123] Compound 2-10 (2.9 g, 2.5 mmol), compound 17-1 (1.5 g, 5.2 mmol), and 5.0 ml of piperidine were added to a 250 mL three-necked flask, and 100 mL of chloroform was added. After replacing the argon gas three times, the temperature was raised to 60 ° C and the reaction was carried out for 12 hours. Cooled to room temperature, the excess solvent was removed by vacuum distillation. The crude product was washed with 100 mL of methanol and filtered. The filter cake was dissolved in dichloromethane and added to silica gel for column chromatography. The eluent was PE: EA = 25: 1 (volume ratio). About 2.6 g of compound (17) was obtained, and the yield was 61.2%. MALDI-TOF-MS: 1696.33.

[0124] Synthesis Example 5: Synthesis of Compound (22)

[0125]

[0126] Synthesis of compound (22):

[0127] Compound 2-10 (2.9 g, 2.5 mmol), compound 22-1 (1.1 g, 5.2 mmol), and 5.0 mL of piperidine were added to a 250 mL three-necked flask, and 100 ml of chloroform was added. After replacing the argon gas three times, the temperature was raised to 60 ° C and the reaction was continued for 12 hours. Cooled to room temperature, the excess solvent was removed by vacuum distillation. The crude product was washed with 120 mL of methanol and filtered. The filter cake was dissolved in dichloromethane and added to silica gel for column chromatography. The eluent was PE:DCM:EA=40:2:1 (volume ratio). About 2.6 g of compound (22) was obtained, with a yield of 68.5%. MALDI-TOF-MS: 1536.38.

[0128] Synthesis Example 6: Synthesis of Compound (31)

[0129]

[0130] Synthesis of compound (31):

[0131] Compound 2-10 (2.9 g, 2.5 mmol), compound 31-1 (1.5 g, 5.2 mmol), and 5.0 mL of piperidine were added to a 250 mL three-necked flask, and 100 mL of chloroform was added. After replacing the argon gas three times, the temperature was raised to 60°C and the reaction was continued for 12 hours. The mixture was cooled to room temperature and the excess solvent was removed by distillation under reduced pressure. The crude product was washed with 120 mL of methanol and filtered. The filter cake was dissolved in dichloromethane and added to silica gel for column chromatography. The eluent was PE:DCM=15:1 (volume ratio). About 3.0 g of compound (31) was obtained, with a yield of 70.7%. MALDI-TOF-MS: 1694.02.

[0132] Synthesis Example 7: Synthesis of Compound (33)

[0133]

[0134] Synthesis of compound 33-2

[0135] Compound 33-1 (46.2 g, 0.2 mol) and 400 mL of anhydrous tetrahydrofuran were added to a 1000 mL three-necked flask in sequence. After replacing argon three times, the temperature was cooled to -78 ° C in a liquid nitrogen ethanol bath. Diisopropylamine lithium (2M, 150 mL) was slowly added to the reaction system. After keeping -78 ° C for 1 hour, compound 7-2 (64.3 g, 0.3 mol) was slowly added to the reaction system. After half an hour, the liquid nitrogen ethanol bath was removed, and the temperature naturally returned to room temperature for 2 hours. The reaction solution was poured into water to quench. Separate the liquids, and extract the aqueous phase twice with ethyl acetate. Combine the organic phases, wash with saturated brine, separate the liquids, dry the organic phase with anhydrous sodium sulfate, and filter. The filtrate was mixed with a sample and dried, and separated by vacuum neutral alumina column chromatography, with dichloromethane as the eluent, to obtain about 65.8 g of compound 33-2, with a yield of 83.6%. MS: 393.65

[0136] Synthesis of compound 33-3

[0137] Compound 33-2 (63.0 g, 160 mmol), 2-4 (23.8 g, 80 mol), tetrakistriphenylphosphine palladium (3.7 g, 3.2 mmol) were added to a 1000 mL three-necked flask, 500 mL of anhydrous toluene was added, argon was replaced three times, and the temperature was raised to 110 ° C for 12 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, water was added to separate, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried by spin drying and separated by silica gel column chromatography. The eluent was PE:DCM = 25:1 (volume ratio), and about 35 g of compound 33-3 was obtained, with a yield of 73.2%. Ms: 597.48 Synthesis of compound 33-4

[0138] Compound 33-3 (29.9 g, 50 mmol) and 400 mL of anhydrous tetrahydrofuran were added to a 1000 mL three-necked flask in sequence. After replacing argon three times, the temperature was cooled to -78 ° C in a liquid nitrogen ethanol bath. N-butyl lithium (2.5 M, 50 mL) was slowly added to the reaction system. After keeping -78 ° C for 1 hour, compound 2-7 (40.7 g, 175 mmol) was slowly added to the reaction system. After half an hour, the ice bath was removed, and the temperature naturally returned to room temperature for 2 hours. The reaction solution was poured into water to quench. The liquid was separated, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried, and separated by vacuum neutral alumina column chromatography, and the eluent was n-hexane, to obtain about 43.7 g of compound 33-4, with a yield of 74.3%. MS: 1175.36.

[0139] Synthesis of compound 33-5

[0140] Compound 33-4 (17.6 g, 15 mmol), 2-3 (21.4 g, 32 mmol), tetrakistriphenylphosphine palladium (1.85 g, 1.6 mmol) were added to a 500 mL three-necked flask, 250 mL of anhydrous toluene was added, argon was replaced three times, and the temperature was raised to 110 ° C for 12 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, water was added to separate, and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine, separated, and the organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was mixed with a sample and dried by spin drying and separated by silica gel column chromatography, and the eluent was PE:DCM = 15:1 (volume ratio), and about 14.1 g of compound 33-5 was obtained, with a yield of 79.6%. MALDI-TOF-MS: 1184.30.

[0141] Synthesis of compound 33-6

[0142] Compound 33-5 (11.8 g, 10 mmol) was added to a 500 ml three-necked flask, and 200 ml of anhydrous DMF was added. After replacing argon three times, the mixture was cooled to 0°C in an ice-salt bath. Phosphorus oxychloride (7.6 g, 50 mmol) was weighed and slowly added dropwise to the reaction system. After the addition was completed, the mixture was stirred at 0°C for 1 hour, and then heated to 80°C for 12 hours. The mixture was cooled to room temperature, poured into water for quenching, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate. The excess solvent was removed by distillation under reduced pressure. Silica gel was added for column chromatography, and the eluent was PE:EA=25:1 (volume ratio). About 8.8 g of compound 33-6 was obtained, with a yield of 70.7%, and MALDI-TOF-MS: 1240.72.

[0143] Synthesis of compound (33):

[0144] Compound 33-6 (3.1 g, 2.5 mmol), compound 33-7 (1.0 g, 5.2 mmol), and 5.0 mL of piperidine were added to a 250 mL three-necked flask, and 100 mL of chloroform was added. After replacing the argon gas three times, the temperature was raised to 60°C and the reaction was continued for 12 h. The mixture was cooled to room temperature and the excess solvent was removed by distillation under reduced pressure. The crude product was washed with 100 mL of methanol and filtered. The filter cake was dissolved in dichloromethane and added to silica gel for column chromatography. The eluent was PE:DCM=10:1 (volume ratio). About 2.7 g of compound (33) was obtained with a yield of 66.9% and MALDI-TOF-MS: 1605.21.

[0145] Application Example 1 Preparation and Characterization of Organic Solar Cell Devices

[0146] The compound prepared in the above example is used as the acceptor material of the photoactive layer to prepare an organic solar cell device, and the device structure is: ITO / PEDOT:PSS / photoactive layer / PFN-Br / Ag, as shown in the schematic diagram Figure 1 As shown, the specific steps include:

[0147] 1) ITO substrate cleaning: The transparent conductive glass with strip-shaped ITO (anode) etched on the surface was cleaned with a cleaning agent, deionized water, acetone and isopropanol ultrasonic oscillation in sequence, dried, and then treated with oxygen plasma for 15 minutes.

[0148] 2) Anode buffer layer preparation: Spin-coat PEDOT:PSS (CLEVIOS TM PVP AI 4083), speed 3000r / min, time 40 seconds, drying at 150℃ for 15 minutes.

[0149] 3) Preparation of photoactive layer: In a glove box (inert gas atmosphere), a photoactive layer material (the donor material is selected from PM6, the acceptor material is selected from the compound (2) prepared in Synthesis Example 1, the mass ratio of PM6 to compound (2) is 1:1, the solvent is chloroform, and the total concentration of the donor and acceptor materials in chloroform is 16 mg / mL) is evenly spin-coated on the anode buffer layer at a spin coating speed of 3000 rpm / min and a spin coating time of 40 seconds to obtain a photoactive layer.

[0150] 4) Preparation of cathode buffer layer: After thermal annealing on a hot plate at 100°C for 10 min, the cathode buffer layer material PFN-Br (PFN-Br was dissolved in methanol to prepare a solution with a concentration of 0.5 mg / mL) was evenly spin-coated on the photoactive layer at a spin coating speed of 2000 rpm / min for 30 s to obtain the cathode buffer layer.

[0151] 5) Cathode layer preparation: In high vacuum (1×10 -6Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of 100 nm.

[0152] 6) Packaging: The device was encapsulated with UV curable resin in a nitrogen glove box.

[0153] Application Example 2-7

[0154] The acceptor material compound (2) in the photoactive layer of Application Example 1 was replaced by compound (7), compound (10), compound (17), compound (22), compound (31), and compound (33), respectively. The other steps were the same as those of Application Example 1. The prepared devices were recorded as Application Examples 2 to 7, as described in Table 1.

[0155] The prepared organic solar cell device was subjected to a performance test. Under the irradiation of AM1.5G standard light of a solar simulator (SS-F5-3A), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated. The specific values ​​are shown in Table 1.

[0156] Table 1 Photoelectric conversion efficiency of solar cell devices prepared in application examples

[0157] Serial number Photoactive layer receptor materials Photoelectric conversion efficiency (%) Application Example 1 Compound (2) 14.71 Application Example 2 Compound (7) 13.25 Application Example 3 Compound (10) 14.26 Application Example 4 Compound (17) 13.80 Application Example 5 Compound (22) 11.39 Application Example 6 Compound (31) 12.67 Application Example 7 Compound (33) 11.10

[0158] As shown in Table 1, the non-condensed ring small molecule materials described in the present invention are applied as photoactive layer materials in organic solar cell devices, and all show good photoelectric conversion efficiency. The reason is that: the non-condensed ring small molecule materials provided by the present invention creatively introduce side chain thiophene groups into the core group thiophene-thiophene, and the S atoms on the side chain thiophene and the N on the main chain thiazole are conformationally locked through the S---N non-covalent bond, thereby effectively restricting the rotation of the CC single bond; in order to further achieve the orderliness of the molecule, at the same time, the present invention further introduces alkoxy substitution on the main chain thiophene, and the S---O non-covalent bond realizes the conformational locking between thiophene and thiazole. Therefore, good molecular stacking and efficient electron transmission are achieved, and then when used as a photoactive layer acceptor material in an organic solar cell device, a higher photoelectric conversion efficiency is achieved.

[0159] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above embodiments. Within the technical concept of the present application, a variety of simple modifications can be made to the technical solution of the present application, and these simple modifications all belong to the protection scope of the present application.

Claims

1. A non-condensed ring small molecule material, It is characterized in that Having a structure as shown in general formula (I): in: R 1 , R 2 , R 3 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -CF 3 、-NO 2 , a straight-chain alkyl group having 1-20 C atoms, a branched-chain alkyl group having 3-20 C atoms, a straight-chain alkoxy group having 1-20 C atoms, a branched-chain alkoxy group having 3-20 C atoms, a straight-chain alkylthio group having 1-20 C atoms, or a branched-chain alkylthio group having 3-20 C atoms; R 4 Each occurrence is independently selected from a straight chain alkyl group having 1-20 C atoms, or a branched chain alkyl group having 3-20 C atoms; Ar 1 and Ar 2 independently selected from unsubstituted or substituted with one or more R * Substituted aromatic radicals having 6-10 carbon atoms, unsubstituted or replaced by one or more R * Substituted heteroaromatic groups having 5 to 10 ring atoms; R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF 3 、-NO 2 , a straight-chain alkyl group having 1-10 C atoms, a branched-chain alkyl group having 3-10 C atoms, a straight-chain alkoxy group having 1-10 C atoms, a branched-chain alkoxy group having 3-10 C atoms, a straight-chain alkylthio group having 1-10 C atoms, or a branched-chain alkylthio group having 3-10 C atoms.

2. The non-condensed ring small molecule material according to claim 1, It is characterized in that Ar 1 and Ar 2 Independently selected from the following groups: Wherein: n1 is independently selected from 0, 1, 2, 3 or 4 at each occurrence; n2 is independently selected from 0, 1, 2, 3, 4, 5 or 6 at each occurrence; n3 is independently selected from 0, 1 or 2 at each occurrence; * indicates a fusion site, which is selected from a C atom.

3. The non-condensed ring small molecule material according to claim 2, It is characterized in that The non-condensed ring small molecule material is selected from any one of the general formulas (II-1) to (II-4):

4. The non-condensed ring small molecule material according to claim 2 or 3, It is characterized in that The R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF 3 、-NO 2 , methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, methoxy, or methylthio.

5. The non-condensed ring small molecule material according to claim 1, It is characterized in that R 1 Each occurrence is independently selected from straight-chain alkyl having 1-16 C atoms, branched-chain alkyl having 3-16 C atoms, straight-chain alkoxy having 1-16 C atoms, branched-chain alkoxy having 3-16 C atoms, straight-chain alkylthio having 1-16 C atoms, or branched-chain alkylthio having 3-16 C atoms; and / or, R 2 , R 3 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, -CF 3 、-NO 2 , a straight-chain alkyl group having 1 to 10 C atoms, a branched-chain alkyl group having 3 to 10 C atoms; and / or, R 4 Each occurrence is independently selected from straight chain alkyl having 4-20 C atoms, or branched chain alkyl having 4-20 C atoms.

6. The non-condensed ring small molecule material according to any one of claims 1 to 3, It is characterized in that R 1 Each occurrence is independently selected from straight-chain alkyl having 1-10 C atoms, branched-chain alkyl having 3-10 C atoms; And R 2 , R 3 Selected from -H.

7. The non-condensed ring small molecule material according to claim 1, It is characterized in that The non-condensed ring small molecule material is selected from the following structures:

8. A mixture comprising a photoactive layer donor material and a photoactive layer acceptor material, It is characterized in that The photoactive layer receptor material is selected from the non-condensed ring small molecule material according to any one of claims 1 to 7.

9. A composition, Features: The composition comprises the non-condensed ring small molecule material according to any one of claims 1 to 7 or the mixture according to claim 8, and at least one organic solvent.

10. An organic solar cell device, comprising at least a cathode, an anode, and a photoactive layer located between the cathode and the anode, It is characterized in that The photoactive layer material comprises the non-condensed ring small molecule material according to any one of claims 1 to 7 or the mixture according to claim 8, or is prepared from the composition according to claim 9.

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