Self-assembled micromolecule material and application thereof

Abstract

The invention relates to the field of organic photoelectric materials, in particular to a self-assembled small molecule material shown in a general formula (I). By introducing a terminal group, the energy level of molecules is adjusted and the accumulation of the molecules is improved, so that the extraction and transmission of holes are improved. When the compound is used as a hole transport layer material to be applied to organic electronic devices, excellent photoelectric properties are shown.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic optoelectronic materials, in particular to a kind of self-assembly small molecule material and application thereof. BACKGROUND

[0002] Organic photovoltaic cells (OPV) have the advantages of light weight, low cost, flexibility and solution preparation. Typical OPV devices adopt a sandwich structure, and the active layer is sandwiched between the hole transport layer and the electron transport layer, so the performance of the transport layer material is very important to improve the performance of the OPV device.

[0003] In traditional OPV positive structure devices, PEDOT:PSS is widely used as a hole transport layer material. However, its defects such as strong acidity and hygroscopicity restrict the performance and long-term stability of the device. The carbazole phosphonic acid small molecule self-assembly material as a hole transport layer material has high efficient charge transport, excellent film forming property, high thermal stability and low cost processing technology, etc., and has attracted wide attention in the field of organic photovoltaic. Self-assembly materials are usually composed of three different parts: anchor group, linking group and terminal group. The anchor group (such as phosphonic acid, carboxylic acid, etc.) forms a stable covalent bond with the hydroxyl (-OH) on the surface of the substrate through its functional group, so as to realize the self-assembly process; the linking group, as a key part connecting the anchor group and the terminal group, is mainly composed of non-conjugated alkyl chain or conjugated aromatic ring, and its main function is to adjust the conjugation degree of the molecule, charge delocalization and molecular packing; the terminal group affects the molecular packing by adjusting the molecular dipole moment and intermolecular force, and also adjusts the energy level, solubility and self-assembly behavior of the material. Although the self-assembly material has many advantages as described above, however, the current traditional carbazole phosphonic acid-based self-assembly material (such as 2PACz) still has the following shortcomings: 1) energy level mismatch: for new active layer materials, the flexibility of 2PACz in matching with the energy level is still limited, which leads to defects in charge transport and limits the efficiency improvement; 2) insufficient dipole moment: the change of work function caused by the small dipole moment is usually limited, which affects the injection barrier; 3) weak intermolecular force: the intermolecular force between the self-assembly small molecule materials is weak, which cannot make them form a dense and ordered packing structure to promote hole transport. Although the introduction of aromatic or heteroaromatic groups into the terminal group can expand the π conjugated system of the molecule and enhance the molecular dipole moment, this strategy often leads to the decrease of the solubility of the molecule and the excessive aggregation of the molecule.

[0004] Therefore, it is urgent to develop a new type of efficient self-assembly material to further improve the photoelectric conversion efficiency of OPV device and improve the market competitiveness of OPV. SUMMARY

[0005] Therefore, the purpose of the present application is to develop a new type of self-assembly small molecule material by introducing The energy level of the molecule is adjusted and the molecule packing is improved, so that the hole extraction and transport are improved. When the compound is applied as a hole transport layer material in an organic photovoltaic device, excellent photoelectric performance is exhibited.

[0006] The first aspect of the present application provides a self-assembled small molecule material having a structure as shown in general formula (I):

[0007] (I)

[0008] wherein: m is selected from 0 or 1;

[0009] L1 is selected from an alkyl group having 1-10 carbon atoms, a substituted or unsubstituted aromatic group having 6-20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms;

[0010] Ar1 is selected from a substituted or unsubstituted aromatic group having 6-20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms;

[0011] Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 6-20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms;

[0012] The "substituted or unsubstituted" defined group is not substituted, or is substituted by one or more substituents R, each occurrence of which is independently selected from -D, halogen, cyano, nitro, an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, an alkylthio group having 1-10 carbon atoms, an aromatic group having 6-20 carbon atoms, a heteroaromatic group having 5-20 ring atoms, or a combination of one or at least two groups of

[0013] L2 is selected from an alkyl group having 1-10 carbon atoms, an aromatic group having 6-20 carbon atoms, a heteroaromatic group having 5-20 ring atoms, or a combination of one or at least two groups of

[0014] * represents a connection site.

[0015] In an alternative embodiment, the Ar1 is selected from a substituted or unsubstituted aromatic group having 6-14 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-14 ring atoms;

[0016] Further, the Ar1 is selected from any one of the following groups:

[0017]

[0018] wherein: ​

[0019] Z is selected from O, S, or Se;

[0020] Y is selected from O, S, Se, CR2R3, or NR4;

[0021] R1is independently selected at each occurrence from -H, -D, halogen, cyano, nitro, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, an alkylthio group having from 1 to 10 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, a heteroaromatic group having from 5 to 20 ring atoms, or a combination of one or at least two of the groups;

[0022] R2, R3, R4are independently selected at each occurrence from -H, -D, an alkyl group having from 1 to 10 carbon atoms, or ;

[0023] # indicates a fused position selected from a C atom.

[0024] In an alternative embodiment, R1is independently selected at each occurrence from -H, -D, halogen, cyano, nitro, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an alkylthio group having from 1 to 6 carbon atoms, an aromatic group having from 6 to 10 carbon atoms, a heteroaromatic group having from 5 to 10 ring atoms, or a combination of one or at least two of the groups.

[0025] In an alternative embodiment, R2, R3are independently selected from an alkyl group having from 1 to 6 carbon atoms.

[0026] In a particular embodiment, R2, R3are independently selected from methyl.

[0027] In an alternative embodiment, R4is selected from .

[0028] In a preferred embodiment, the self-assembled small molecule material according to the present application has any of the structures as shown in general formulae (II-1) to (II-6):

[0029] .

[0030] In a preferred embodiment, Ar2, Ar3are independently selected from a substituted or unsubstituted aromatic group having from 6 to 10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having from 5 to 10 ring atoms.

[0031] Further, Ar2, Ar3are independently selected from any of the following groups:

[0032]

[0033] wherein:

[0034] W is independently selected at each occurrence from O, S, or Se;

[0035] R2is independently selected at each occurrence from -D, -F, -Cl, -Br, -I, cyano, nitro, methyl, ethyl, isopropyl, t-butyl, or methoxy;

[0036] n1is selected from 0, 1, 2, 3, 4, or 5; n2is selected from 0, 1, 2, or 3; n3is selected from 0, 1, 2, 3, 4, 5, 6, or 7; and n4is selected from 0, 1, 2, 3, or 4.

[0037] In an alternative embodiment, Ar2and Ar3in Formula (II-1), Formula (II-6) are selected from the same group.

[0038] In a particular embodiment, Formula (II-1) is selected from any one of the following structures:

[0039] .

[0040] In a particular embodiment, Formula (II-6) is selected from any one of the following structures:

[0041] .

[0042] In a particular embodiment, R2is independently selected at each occurrence from -D, -F, -Cl, -Br, -I, cyano, nitro, methyl, ethyl, isopropyl, t-butyl, or methoxy.

[0043] In an alternative embodiment, L1is selected from a straight chain alkyl group having 1-10 carbon atoms.

[0044] In a particular embodiment, L1is selected from , or .

[0045] In another alternative embodiment, L1is selected from a substituted or unsubstituted aromatic group having 6-10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-10 ring atoms.

[0046] In another particular embodiment, L1is selected from , , or .

[0047] In a certain alternative embodiment, L2is selected from a linear alkyl group having 1-10 carbon atoms.

[0048] In a certain specific embodiment, L2is selected from , or .

[0049] In another alternative embodiment, L2is selected from a substituted or unsubstituted aromatic group having 6-10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-10 ring atoms.

[0050] In another specific embodiment, L2is selected from , , or .

[0051] The self-assembled small molecule materials according to the present application are selected from the following structures, but are not limited thereto:

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] .

[0067] The second aspect of the present application relates to an organic electronic device, comprising a cathode, an anode, a photoactive layer between the cathode and the anode, and a hole transport layer between the anode and the photoactive layer, the hole transport layer material being selected from the self-assembled small molecule material as described in the first aspect.

[0068] The method for preparing the hole transport layer is to dissolve the self-assembled small molecule material in an alcohol organic solvent (such as methanol, ethanol, isopropanol, etc.) or dimethylformamide (DMF) to prepare a hole transport material solution with a concentration of 0.1-2 mg / mL, and then to prepare the solution on the anode layer by printing, which includes but is not limited to spin coating, blade coating, etc.

[0069] In a preferred embodiment, the organic electronic device is selected from an organic photovoltaic device, a perovskite solar cell, or a perovskite-organic tandem solar cell.

[0070] In a specific embodiment, the organic electronic device is selected from an organic photovoltaic device.

[0071] In an embodiment, the photoactive layer material comprises a photoactive layer donor material and a photoactive layer acceptor material.

[0072] In an embodiment, the photoactive layer donor material is selected from a polymeric donor material. The polymeric donor material can be selected from a polythiophene material system, such as P3AT, P3HT, P3OT, P3DDT, etc.; a fluorene-containing polymeric material system, such as PF8BT, etc.; a novel structure narrow-bandgap polymeric material system, such as benzo-dithiophene (BDT), benzo-thiadiazole (BT, BBT), quinoxaline (QU, PQ), pyrazine (TP, PQ), and electron-rich groups (such as thiophene derivatives) copolymerized, such as PM6, PM7, PBDB-T, D18, D18-Cl, PTQ10, PTQ11, PBQx-TCl, PBQx-TF, PB2, etc., but not limited thereto.

[0073] In an embodiment, the photoactive layer acceptor material is selected from one or more of: an ITIC-configuration-based acceptor material, including but not limited to ITIC, ITIC-4F, ITIC-4Cl, ITIC-2F, ITIC-M, ITCC, ITCC-Cl, etc.; a Y-type acceptor material, including but not limited to Y6, L8-BO, BTP-eC9, N3, N4, Y6-O, HDO-4Cl, BTP-H2, PY-IT, etc.; an FCC-type acceptor material, including but not limited to FCC-Cl, FTCC-Br, etc.; a fullerene acceptor material, including but not limited to PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerene, etc.

[0074] The selection of the acceptor material in the active layer can also be further referenced in the literature: Chem. Rev. 2022, 122, 18, 14180-14274.

[0075] At least one of the anode and the cathode is transparent or semi-transparent to facilitate light incidence. The material used to prepare the electrode 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, etc.; conductive nanomaterials, such as metal nanowires, nanoparticle paste, 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 multi-layer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al / Li, Al / BaF2, and Al:BaF2:Ba, etc., but not limited thereto.

[0076] Further, the organic electronic device according to the present application further comprises an electron transport layer, which is located between the cathode and the photoactive layer.

[0077] Preferably, the electron transport layer material can be selected from low work function metal complexes, metal oxides, metal salts, etc., such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, PEI-Zn, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; and can also be a polymer material, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but not limited thereto.

[0078] Further, the organic photovoltaic device further comprises a substrate. In one embodiment, the substrate is disposed on one side of the anode and on a different side from the photoactive layer. In another embodiment, the substrate is disposed on one side of the cathode and on a different side from the photoactive layer.

[0079] In one embodiment, as the substrate, a substrate having excellent transparency, surface smoothness, handleability, and water resistance can be used. Specifically, a glass substrate, a thin film glass substrate, or a transparent plastic substrate can be used. The plastic substrate can include a film in a single layer or a multi-layer form such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), polyimide (PI), Parylene, etc., but is not limited thereto, and a substrate commonly used for an organic solar cell can also be used.

[0080] The organic photovoltaic device according to the present application is mainly used in the fields of indoor photovoltaic, wearable devices, smart internet of things, smart home, smart agriculture, building photovoltaic, new energy vehicles, etc.

[0081] The present application protects a self-assembled small molecule material as shown in general formula (I), by introducing The material is used as a hole transport material for preparing a hole transport layer, and shows excellent film forming property, high efficient hole extraction and transport performance, thereby effectively improving the photoelectric conversion efficiency of the device. BRIEF DESCRIPTION OF DRAWINGS

[0082] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed in the specific embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0083] Figure 1 The structure of the organic photovoltaic device in the device embodiment is shown in the figure. DETAILED DESCRIPTION

[0084] In order to make the purpose, technical scheme and effect of the present application more clear and definite, the present application will be further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and not to limit the present application. Based on the described embodiments of the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application.

[0085] The selection range of the terms "and / or", "or / and", "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, including any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least two conjunctions selected from "and / or", "or / and", "and / or" are combined to connect at least three items, it should be understood that in this application, the technical solution undoubtedly includes the technical solution connected by "logical and", and also undoubtedly includes the technical solution connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C and D (i.e. the technical solution connected by "logical or"), and also includes any and all combinations of A, B, C and D, i.e. includes the combination of any two or any three of A, B, C and D, and also includes the four-item combination of A, B, C and D (i.e. the technical solution connected by "logical and").

[0086] In the present application, organic photovoltaic device, organic photovoltaic cell, organic solar cell, OPV, OSC have the same meaning and can be interchangeable.

[0087] In the present application, photoactive layer, active layer have the same meaning and can be interchangeable.

[0088] In the present application, when the same group contains multiple substituents with the same symbol, each substituent can be the same as or different from each other, for example The six Rs on the benzene ring can be the same as or different from each other.

[0089] In the present application, "substituted" means that one or more hydrogen atoms in the substituent is replaced by a substituent.

[0090] In the present application, "ring atom number" means the number of atoms in the ring itself of a structural compound obtained by bonding atoms into a ring (e.g., monocyclic compound, fused ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound). When the ring is substituted by a substituent, the atoms included in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below, unless otherwise specified. In an aromatic group, the ring atom number is the same as the carbon atom number; in a heteroaromatic group, the ring atom number is the carbon atom number plus the number of heteroatoms; for example, the ring atom number of a benzene ring is 6, the ring atom number of a naphthalene ring is 10, the ring atom number of quinoline is 10, the ring atom number of a thienyl group is 5, and the ring atom number of thienothiophene is 8.

[0091] In the present application, "aromatic group" refers to an optionally functionalized or substituted group derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group, in other words, the aromatic group can be a monocyclic aromatic group, a fused ring aromatic group, two or more monocyclic aromatic groups linked by a carbon-carbon bond in conjugation, a monocyclic aromatic group and a fused ring aromatic group linked by a carbon-carbon bond in conjugation, two or more fused ring aromatic groups linked by a carbon-carbon bond in conjugation. That is, unless otherwise specified, two or more aromatic groups linked by a carbon-carbon bond in conjugation can also be considered as an aromatic group of the present application. Preferably, the aromatic group is selected from the group consisting of aromatic groups having 6 to 20 C atoms; further, the aromatic group is selected from the group consisting of aromatic groups having 6 to 10 C atoms. The aromatic group includes, but is not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthenyl, and derivatives thereof.

[0092] In the present application, "heteroaromatic group" refers to a heteroaromatic ring comprising 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring or a derivative thereof, the heteroatom can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The term "heteroaromatic group" as used herein also includes a group in which one or more heteroaromatic groups are fused with one or more aromatic, aliphatic or heterocyclic rings. Preferably, the heteroaromatic group is selected from the group consisting of heteroaromatic groups having 5 to 20 ring atoms; further, the heteroaromatic group is selected from the group consisting of heteroaromatic groups having 5 to 10 ring atoms. The heteroaromatic group includes, but is not limited to, thienyl, furanyl, selenolyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolyl, quinoxalyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furanopyrrolyl, furanofuranyl, thienofuranyl, and derivatives thereof.

[0093] In the present application, the alkyl group is selected from the group consisting of linear alkyl, branched alkyl, cyclic alkyl, and combinations thereof, the number of carbon atoms of the linear alkyl group can be 1 to 10, or 1 to 6. The number of carbon atoms of the branched alkyl group can be 3 to 10, or 3 to 6. The number of carbon atoms of the cyclic alkyl group can be 3 to 10, or 3 to 6.

[0094] The term "alkoxy" refers to a group of the structure "-O-alkyl", i.e., an alkyl group as defined above attached to another group through an oxygen atom. The linear alkoxy group means that the alkyl group in "-O-alkyl" is selected from linear alkyl, wherein the number of carbon atoms of the linear alkyl group can be 1 to 10 or 1 to 6; the branched alkoxy group means that the alkyl group in "-O-alkyl" is selected from branched alkyl, wherein the number of carbon atoms of the branched alkyl group can be 3 to 10 or 3 to 6.

[0095] The term "alkylthio" refers to a group of structure "-S-alkyl", i.e. an alkyl group as defined above attached to the other group via a sulfur atom. Straight-chain alkylthio means that the alkyl group in "-S-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms of the straight-chain alkyl group can be 1 to 10 or 1 to 6; branched alkylthio means that the alkyl group in "-S-alkyl" is selected from branched alkyl groups, wherein the number of carbon atoms of the branched alkyl group can be 3 to 10 or 3 to 6.

[0096] In the present application, when the connecting position in a group is not specified, it means that the optional connecting position in the group is connected as the connecting position.

[0097] In the present application, "independently selected from" one or more groups means that when one or more groups are simultaneously present in a compound and at multiple places, they are all independently selected, which can be the same or different.

[0098] In the present application, a single bond to which a substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to the optional position of the ring, for example R is connected to any substitutable position of the phenyl ring.

[0099] In the description of the structural elements of the present application, the words "comprising" or "including" and the like used in the present application mean that the devices or materials appearing before the word are encompassed by the devices or materials listed after the word and their equivalents, and other devices or materials are not excluded.

[0100] In the description of the present application, it should be understood that the terms "upper", "lower", "between layers" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship commonly used when the organic solar cell device is placed, or the orientation or positional relationship commonly understood by those skilled in the art, and are only for the convenience of describing the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application.

[0101] As used in the present application, "combinations thereof", "any combination thereof", "any combination manner thereof", "combination" and the like include all suitable combinations of any two, any three or more of the listed groups.

[0102] In the present application, "further", "still further", "in particular" and the like are used for the purpose of description, indicating differences in content, but should not be understood as limiting the scope of protection of the present application.

[0103] In the present application, "optionally", "optional" and "option" mean that it can be present or absent, i.e. selected from either of the two parallel schemes "present" or "absent". If there are multiple "options" in a technical solution, and there is no special description, no contradiction or mutual restriction, each "option" is independent.

[0104] In the present application, the technical features described in an open manner include both the closed technical solution consisting of the listed features and the open technical solution containing the listed features.

[0105] Synthesis of self-assembled small molecules

[0106] The following examples facilitate better understanding of the disclosure of the present application and are not intended to limit it in any way. The experimental methods used in the following examples are conventional methods unless otherwise specified, and the materials, reagents, etc. used are conventional methods unless otherwise specified, and can be obtained commercially.

[0107] Synthesis Example 1: Synthesis of compound (3)

[0108]

[0109] Synthesis of compound 3-a:

[0110] Under nitrogen atmosphere, 3,6-dibromocarbazole (1.95 g, 6 mmol), deuterated phenol (1.31 g, 13.2 mmol) were added to 30 mL of toluene solution and stirred, then potassium phosphate (5.09 g, 24 mmol) and cuprous iodide (0.23 g, 1.2 mmol) were added, and the reaction was stirred at 110°C overnight. After the raw material completely reacted, the reaction liquid was cooled to room temperature, quenched with water, extracted with dichloromethane, and the organic phases were combined and washed with water three times. After drying with anhydrous sodium sulfate, the excess solvent was removed by reduced pressure distillation, and column chromatography was used for purification, with petroleum ether:dichloromethane = 3:1 (volume ratio) as the eluent, to obtain about 0.97 g of compound 3-a, with a yield of 44.7%. MS: 361.82.

[0111] Synthesis of compound 3-b:

[0112] Accurately weigh compound 3-a (0.95 g, 2.63 mmol) into a three-necked flask with 1,4-dibromobutane (20 mL), add tetrabutylammonium bromide (0.25 g, 0.79 mmol) and 50% potassium hydroxide aqueous solution (5 mL), and warm to 70°C for 4 hours. After the raw material is completely reacted, cool the reaction solution to room temperature, quench with water, extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, remove the excess solvent under reduced pressure, purify by column chromatography, and elute with petroleum ether:dichloromethane=8:1 (volume ratio) to obtain about 0.93 g of compound 3-b, with a yield of 71.3%. MS: 496.21.

[0113] Synthesis of compound 3-c:

[0114] Under a nitrogen atmosphere, add compound 3-b (0.9 g, 1.81 mmol) to a three-necked flask with triethyl phosphite (10 mL), and stir at 180°C for 3 hours. After the raw material is completely reacted, cool the reaction solution to room temperature, quench with saturated ammonium chloride aqueous solution, extract with dichloromethane, combine the organic phases, wash with water three times. Dry over anhydrous sodium sulfate, remove the excess solvent under reduced pressure, purify by column chromatography, and elute with petroleum ether:ethyl acetate=1:1 (volume ratio) to obtain about 0.85 g of compound 3-c, with a yield of 84.7%. MS: 554.16.

[0115] Synthesis of compound (3):

[0116] Accurately weigh compound 3-c (0.8 g, 1.44 mmol) into 20 mL of 1,4-dioxane, stir, introduce nitrogen for 30 minutes, and drop trimethylsilyl bromide (0.8 mL), warm to 70°C, and stir overnight. After the raw material is completely reacted, remove most of the solvent under reduced pressure, quench with water, and precipitate a large amount of white solid. Filter the solid, recrystallize from tetrahydrofuran, and obtain about 0.54 g of compound (3), with a yield of 75.4%. MALDI-TOF-MS: 497.58.

[0117] Synthesis Example 2: Synthesis of compound (6)

[0118]

[0119] Synthesis of compound 6-a:

[0120] Accurately weigh 3,6-dibromo-carbazole (1.95 g, 6 mmol), 4-fluorophenol (1.48 g, 13.2 mmol) into a three-neck flask with 30 mL of toluene, then add potassium phosphate (5.09 g, 24 mmol) and cuprous iodide (0.23 g, 1.2 mmol), and stir under nitrogen for 30 minutes, then heat to 110°C and stir overnight. After the raw material is completely reacted, cool the reaction solution to room temperature, quench with water, then extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography with petroleum ether:dichloromethane = 4:1 (volume ratio) as the eluent to obtain about 0.84 g of compound 6-a, with a yield of 36.1%. MS: 387.63.

[0121] Synthesis of compound 6-b:

[0122] Under a nitrogen atmosphere, compound 6-a (0.83 g, 2.14 mmol) is dissolved in 1,2-dibromoethane (20 mL), then tetrabutylammonium bromide (0.21 g, 0.64 mmol) and 50% potassium hydroxide aqueous solution (5 mL) are added, and the reaction is heated to 70°C for four hours. After the raw material is completely reacted, cool the reaction solution to room temperature, quench with water, then extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography with petroleum ether:dichloromethane = 20:1 (volume ratio) as the eluent to obtain about 0.95 g of compound 6-b, with a yield of 89.8%. MS: 494.29.

[0123] Synthesis of compound 6-c:

[0124] Under a nitrogen atmosphere, compound 6-b (0.94 g, 1.90 mmol) and triethyl phosphite (10 mL) are added to a 50 mL three-neck flask, and the reaction is stirred at 180°C for three hours. After the raw material is completely reacted, cool the reaction solution to room temperature, then quench with saturated ammonium chloride aqueous solution, extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography with petroleum ether:ethyl acetate = 1:1 (volume ratio) as the eluent to obtain about 0.88 g of compound 6-c, with a yield of 84.1%. MS: 551.02.

[0125] Synthesis of compound (6):

[0126] Accurately weighed compound 6-c (0.77 g, 1.40 mmol) was dissolved in 20 mL of 1,4-dioxane, and nitrogen was bubbled for 30 minutes. Then, trimethylsilyl bromide (0.77 mL) was added dropwise, and the reaction was stirred at 70°C overnight. After the starting material was completely reacted, most of the solvent was removed by distillation under reduced pressure. After quenching with water, a large amount of white solid was precipitated. The solid was filtered, and compound (6) was obtained by recrystallization from tetrahydrofuran in a yield of about 0.52 g (74.9%). MALDI-TOF-MS: 495.76.

[0127] Synthesis Example 3: Synthesis of compound (9)

[0128]

[0129] Synthesis of compound 9-a:

[0130] Accurately weighed 3,6-dibromo-carbazole (1.95 g, 6 mmol) and thiophene-2-ol (1.32 g, 13.2 mmol) were dissolved in 30 mL of toluene, and potassium phosphate (5.09 g, 24 mmol) and cuprous iodide (0.23 g, 1.2 mmol) were added. Nitrogen was bubbled for 30 minutes, and the reaction was stirred at 110°C overnight. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and water was added to quench the reaction. The reaction mixture was extracted with dichloromethane, and the combined organic phase was washed with water three times. After drying with anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure. Compound 9-a was obtained by column chromatography using petroleum ether:dichloromethane = 6:1 (volume ratio) as an eluent in a yield of about 1.08 g (49.5%). MS: 363.44.

[0131] Synthesis of compound 9-b:

[0132] Accurately weighed compound 9-a (1.0 g, 2.75 mmol) was added to a three-necked flask containing 1,2-dibromoethane (20 mL), and tetrabutylammonium bromide (0.27 g, 0.83 mmol) and 50% potassium hydroxide aqueous solution (5 mL) were added. Nitrogen was bubbled for 30 minutes, and the reaction was stirred at 70°C for four hours. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and water was added to quench the reaction. The reaction mixture was extracted with dichloromethane, and the combined organic phase was washed with water three times. After drying with anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure. Compound 9-b was obtained by column chromatography using petroleum ether:dichloromethane = 12:1 (volume ratio) as an eluent in a yield of about 0.94 g (72.6%). MS: 470.65.

[0133] Synthesis of compound 9-c:

[0134] Compound 9-b (0.9 g, 1.91 mmol), triethyl phosphite (10 mL) were added into a 50 mL three-necked flask under nitrogen atmosphere, and stirred at 180 °C for 3 hours. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with saturated aqueous ammonium chloride solution, extracted with dichloromethane, and the combined organic phase was washed with water for three times. After drying over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and then purified by column chromatography with petroleum ether: ethyl acetate = 1:1 (volume ratio) as eluent to give compound 9-c about 0.86 g in 85.4% yield. MS: 527.36.

[0135] Synthesis of compound (9):

[0136] Compound 9-c (0.76 g, 1.45 mmol) was accurately weighed and dissolved in 20 mL of 1,4-dioxane, and then nitrogen was bubbled for 30 minutes. Trimethylsilyl bromide (0.76 mL) was added dropwise, and the reaction was stirred at 70 °C overnight. After the starting material was completely reacted, most of the solvent was removed by distillation under reduced pressure, and then quenched with water to precipitate a large amount of white solid. The solid was filtered and recrystallized from tetrahydrofuran to give compound (9) about 0.45 g in 65.8% yield. MALDI-TOF-MS: 471.97.

[0137] Synthesis Example 4: Synthesis of compound (21)

[0138]

[0139] Synthesis of compound 21-a:

[0140] 9H-carbazole-3,6-diol (1.19 g, 6 mmol), 2-bromothiophene[3,2-b]thiophene (2.89 g, 13.2 mmol) were added into a 30 mL N,N-dimethylformamide solution under nitrogen atmosphere, and then potassium carbonate (4.95 g, 36 mmol) was added, and the reaction was stirred at 110 °C for 5 hours. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with water, extracted with dichloromethane, and the combined organic phase was washed with water for three times. After drying over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and then purified by column chromatography with petroleum ether: dichloromethane = 2:1 (volume ratio) as eluent to give compound 21-a about 1.11 g in 38.9% yield. MS: 475.52.

[0141] Synthesis of compound 21-b:

[0142] Accurately weigh compound 21-a (1.0 g, 2.1 mmol) into a three-necked flask with 1,4-dibromobutane (20 mL), add tetrabutylammonium bromide (0.2 g, 0.63 mmol) and 50% potassium hydroxide aqueous solution (5 mL), and warm to 70°C for 4 hours. After the raw material is completely reacted, cool the reaction solution to room temperature, quench with water, extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, remove the excess solvent under reduced pressure, purify by column chromatography, and elute with petroleum ether:dichloromethane=10:1 (volume ratio) to obtain about 1.07 g of compound 21-b, with a yield of 83.5%. MS: 610.88.

[0143] Synthesis of compound 21-c:

[0144] Under a nitrogen atmosphere, add compound 21-b (0.91 g, 1.5 mmol) to a three-necked flask with triethyl phosphite (12 mL), and stir at 180°C for 3 hours. After the raw material is completely reacted, cool the reaction solution to room temperature, quench with saturated ammonium chloride aqueous solution, extract with dichloromethane, combine the organic phases, wash with water three times. Dry over anhydrous sodium sulfate, remove the excess solvent under reduced pressure, purify by column chromatography, and elute with petroleum ether:ethyl acetate=2:1 (volume ratio) to obtain about 0.85 g of compound 21-c, with a yield of 84.9%. MS: 667.59.

[0145] Synthesis of compound (21):

[0146] Accurately weigh compound 21-c (0.80 g, 1.2 mmol) into 20 mL of 1,4-dioxane, stir, and pass nitrogen for 30 minutes. Add trimethylsilyl bromide (0.8 mL), warm to 70°C, and stir overnight. After the raw material is completely reacted, remove most of the solvent under reduced pressure, quench with water, and precipitate a large amount of white solid. Filter the solid, recrystallize from tetrahydrofuran, and obtain about 0.42 g of compound (21), with a yield of 57.2%. MALDI-TOF-MS: 611.74.

[0147] Synthesis Example 5: Synthesis of compound (26)

[0148]

[0149] Synthesis of compound 26-a:

[0150] Accurately weigh 3,6-dibromo-carbazole (1.95 g, 6 mmol), thiophen-3-ol (1.32 g, 13.2 mmol) into 30 mL of toluene, and stir to dissolve. Add potassium phosphate (5.09 g, 24 mmol) and cuprous iodide (0.23 g, 1.2 mmol), and stir at 110°C for 12 hours under nitrogen. After the starting material is completely reacted, cool the reaction solution to room temperature, add water to quench the reaction, and extract with dichloromethane. Wash the combined organic phase with water three times, dry over anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Purify by column chromatography using petroleum ether:dichloromethane = 6:1 (volume ratio) as the eluent to obtain about 1.12 g of compound 26-a at a yield of 51.4%. MS: 363.44.

[0151] Synthesis of compound 26-b:

[0152] Accurately weigh compound 26-a (1.10 g, 3.03 mmol), 1,4-dibromo-benzene (3.57 g, 15.15 mmol) into 20 mL of toluene, and add potassium tert-butoxide (1.01 g, 9.09 mmol). Stir for 30 minutes under nitrogen, and then quickly add tris(dibenzylideneacetone)dipalladium (0.08 g, 0.09 mmol) and tri-tert-butylphosphonium tetrafluoroborate (0.21 g, 0.72 mmol), and stir at 120°C for 12 hours. After the starting material is completely reacted, cool the reaction solution to room temperature, add water to quench the reaction, and extract with dichloromethane. Wash the combined organic phase with water three times, dry over anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Purify by column chromatography using petroleum ether:dichloromethane = 9:1 (volume ratio) as the eluent to obtain about 0.96 g of compound 26-b at a yield of 61.2%. MS: 518.36.

[0153] Synthesis of compound 26-c:

[0154] Under a nitrogen atmosphere, add compound 26-b (0.93 g, 1.80 mmol) and triethyl phosphite (10 mL) into a 50 mL three-necked flask, and stir at 180°C for 3 hours. After the starting material is completely reacted, cool the reaction solution to room temperature, add saturated aqueous ammonium chloride to quench the reaction, and extract with dichloromethane. Wash the combined organic phase with water three times, dry over anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Purify by column chromatography using petroleum ether:dichloromethane = 1:2 (volume ratio) as the eluent to obtain about 0.78 g of compound 26-c at a yield of 75.3%. MS: 575.69.

[0155] Synthesis of compound (26):

[0156] Accurately weigh compound 26-c (0.75 g, 1.3 mmol) into a 20 mL of 1,4-dioxane, and then nitrogen was bubbled for 30 min. Trimethylsilyl bromide (0.75 mL) was added dropwise, and the reaction was stirred at 70 °C overnight. After the starting material was completely reacted, most of the solvent was removed by distillation under reduced pressure. After quenching with water, a large amount of white solid was precipitated. The solid was filtered and recrystallized from tetrahydrofuran to obtain compound (26) about 0.37 g, yield 54.8%. MALDI-TOF-MS: 519.38.

[0157] Synthesis Example 6: Synthesis of compound (35)

[0158]

[0159] Synthesis of compound 35-a:

[0160] Accurately weigh 10-bromo-7H-benzo[C]carbazole (1.78 g, 6 mmol) and phenol (0.86 g, 9 mmol) into 30 mL of toluene, and then stirred to dissolve. Potassium phosphate (2.54 g, 12 mmol) and cuprous iodide (0.11 g, 0.6 mmol) were added, and then nitrogen was bubbled for 30 min. The reaction was stirred at 110 °C overnight. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with water. The organic phase was extracted with dichloromethane, and then combined and washed with water three times. After drying with anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure. Purification was performed by column chromatography using petroleum ether: dichloromethane = 5:1 (volume ratio) as the eluent to obtain compound 35-a about 1.22 g, yield: 65.8%. MS: 309.21.

[0161] Synthesis of compound 35-b:

[0162] Accurately weigh compound 35-a (1.20 g, 3.88 mmol) into a three-necked flask containing 1,4-dibromobutane (25 mL), and then add tetrabutylammonium bromide (0.37 g, 1.16 mmol) and 50% aqueous potassium hydroxide solution (6 mL). Nitrogen was bubbled for 30 min, and then the reaction was stirred at 70 °C for four hours. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with water. The organic phase was extracted with dichloromethane, and then combined and washed with water three times. After drying with anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure. Purification was performed by column chromatography using petroleum ether: dichloromethane = 7:1 (volume ratio) as the eluent to obtain compound 35-b about 1.13 g, yield: 65.7%. MS: 443.45.

[0163] Synthesis of compound 35-c:

[0164] Compound 35-b (1.10 g, 2.48 mmol), triethyl phosphite (12 mL) were added into a 50 mL three-necked flask under nitrogen atmosphere, and the reaction was stirred at 180 °C for 3 h. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with saturated aqueous ammonium chloride solution, extracted with dichloromethane, and the combined organic phase was washed with water for three times. After drying over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and then purified by column chromatography with petroleum ether:dichloromethane = 1:3 (volume ratio) as the eluent to give compound 35-c about 0.88 g in 70.7% yield. MS: 501.67.

[0165] Synthesis of compound (35):

[0166] Compound 35-c (0.85 g, 1.70 mmol) was accurately weighed and dissolved in 20 mL of 1,4-dioxane, and then nitrogen was bubbled for 30 min. Trimethylsilyl bromide (0.85 mL) was added dropwise, and the reaction was stirred at 70 °C overnight. After the starting material was completely reacted, most of the solvent was removed by distillation under reduced pressure, and then quenched with water to precipitate a large amount of white solid. The solid was filtered and recrystallized from tetrahydrofuran to give compound (35) about 0.46 g in 60.7% yield. MALDI-TOF-MS: 445.50.

[0167] Synthesis Example 7: Synthesis of compound (41)

[0168]

[0169] Synthesis of compound 41-a:

[0170] 2-Bromo-5H-benzocarbazole (1.78 g, 6 mmol), thiophen-2-ol (0.9 g, 9 mmol) were accurately weighed and dissolved in 25 mL of toluene, and then potassium phosphate (2.54 g, 12 mmol) and cuprous iodide (0.11 g, 0.6 mmol) were added. Nitrogen was bubbled for 30 min, and then the reaction was stirred at 110 °C overnight. After the starting material was completely reacted, the reaction solution was cooled to room temperature, quenched with water, extracted with dichloromethane, and the combined organic phase was washed with water for three times. After drying over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and then purified by column chromatography with petroleum ether:dichloromethane = 8:1 (volume ratio) as the eluent to give compound 41-a about 0.97 g in 51.2% yield. MS: 315.58.

[0171] Synthesis of compound 41-b:

[0172] Accurately weighed compound 41-a (0.95 g, 3.01 mmol) was added to a three-necked flask with 1,2-dibromoethane (20 mL), tetrabutylammonium bromide (0.29 g, 0.9 mmol) and 50% potassium hydroxide aqueous solution (5 mL), and the mixture was stirred at 70 °C for 4 h under nitrogen atmosphere. After the starting material was completely consumed, the reaction mixture was cooled to room temperature, quenched with water, and extracted with dichloromethane. The organic phase was combined and washed with water three times. After drying over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and the product was purified by column chromatography using petroleum ether:dichloromethane (11:1, by volume) as the eluent to give compound 41-b about 0.90 g in 70.7% yield. MS: 422.82.

[0173] Synthesis of compound 41-c:

[0174] Compound 41-b (0.85 g, 2.0 mmol) and triethyl phosphite (10 mL) were added to a 50 mL three-necked flask and stirred at 180 °C for 3 h under nitrogen atmosphere. After the starting material was completely consumed, the reaction mixture was cooled to room temperature, quenched with saturated ammonium chloride aqueous solution, and extracted with dichloromethane. The organic phase was combined and washed with water three times. After drying over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and the product was purified by column chromatography using petroleum ether:ethyl acetate = 1:2 (by volume) as the eluent to give compound 41-c about 0.74 g in 77.1% yield. MS: 479.60.

[0175] Synthesis of compound (41):

[0176] Compound 41-c (0.72 g, 1.5 mmol) was dissolved in 20 mL of 1,4-dioxane, and stirred at 70 °C for overnight after nitrogen was bubbled through the solution for 30 min and trimethylsilyl bromide (0.72 mL) was added dropwise. After the starting material was completely consumed, the excess solvent was removed by distillation under reduced pressure, and the product was obtained as a white solid after quenching with water. The solid was recrystallized from tetrahydrofuran to give compound (9) about 0.39 g in 61.4% yield. MALDI-TOF-MS: 423.35.

[0177] Synthesis of compound (46):

[0178]

[0179] Synthesis of compound 46-a:

[0180] Accurately weigh 12-bromo-9H-dibenzo[a,c]carbazole (2.08 g, 6 mmol) and phenol (0.86 g, 9 mmol) into 30 mL of toluene and stir to dissolve, then add potassium phosphate (2.54 g, 12 mmol) and cuprous iodide (0.11 g, 0.6 mmol), and pass nitrogen for 30 minutes, then raise the temperature to 110°C and stir overnight. After the raw material is completely reacted, cool the reaction liquid to room temperature, quench with water, then extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography, using petroleum ether:dichloromethane = 4:1 (volume ratio) as the eluent, to obtain about 0.99 g of compound 46-a, with a yield of 45.9%. MS: 359.45.

[0181] Synthesis of compound 46-b:

[0182] Accurately weigh compound 46-a (0.98 g, 2.73 mmol) into a three-necked flask containing 1,4-dibromobutane (20 mL), then add tetrabutylammonium bromide (0.26 g, 0.82 mmol) and 50% potassium hydroxide aqueous solution (5 mL), pass nitrogen for 30 minutes, then raise the temperature to 70°C and react for four hours. After the raw material is completely reacted, cool the reaction liquid to room temperature, quench with water, then extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography, using petroleum ether:dichloromethane = 5:1 (volume ratio) as the eluent, to obtain about 1.14 g of compound 46-b, with a yield of 84.4%. MS: 494.51.

[0183] Synthesis of compound 46-c:

[0184] Under a nitrogen atmosphere, add compound 46-b (1.1 g, 2.22 mmol) and triethyl phosphite (15 mL) into a 50 mL three-necked flask, and stir to react at 180°C for three hours. After the raw material is completely reacted, cool the reaction liquid to room temperature, then quench with saturated ammonium chloride aqueous solution, extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography, using petroleum ether:dichloromethane = 1:5 (volume ratio) as the eluent, to obtain about 0.83 g of compound 46-c, with a yield of 67.8%. MS: 551.68.

[0185] Synthesis of compound (46):

[0186] Accurately weigh compound 46-c (0.77 g, 1.4 mmol) into a 20 mL of 1,4-dioxane, and then nitrogen was bubbled for 30 min. Trimethylsilyl bromide (0.77 mL) was added dropwise, and the reaction was stirred at 70 °C overnight. After the starting material was completely reacted, most of the solvent was removed by distillation under reduced pressure. After quenching with water, a large amount of white solid was precipitated. The solid was filtered and recrystallized from tetrahydrofuran to obtain compound (35) about 0.39 g, yield 56.2%. MALDI-TOF-MS: 495.71.

[0187] Synthesis Example 9: Synthesis of compound (57)

[0188]

[0189] Synthesis of compound 57-a:

[0190] Accurately weigh 2-bromo-5H-[1]benzothieno[3,2-c]carbazole (2.11 g, 6 mmol), thiophene-2-ol (0.9 g, 9 mmol) into 25 mL of toluene, and then stirred to dissolve. Potassium phosphate (2.54 g, 12 mmol) and cuprous iodide (0.11 g, 0.6 mmol) were added, and then nitrogen was bubbled for 30 min. The reaction was stirred at 110 °C overnight. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with water. The organic phase was extracted with dichloromethane, and then washed with water three times. After drying with anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure. Purification was performed by column chromatography using petroleum ether: dichloromethane = 6:1 (volume ratio) as an eluent to obtain compound 57-a about 1.33 g, yield: 59.7%. MS: 371.45.

[0191] Synthesis of compound 57-b:

[0192] Accurately weigh compound 57-a (1.31 g, 3.53 mmol) into a three-necked flask containing 1,4-dibromobutane (30 mL), and then add tetrabutylammonium bromide (0.34 g, 1.06 mmol) and 50% aqueous potassium hydroxide solution (7 mL). Nitrogen was bubbled for 30 min, and then the reaction was stirred at 70 °C for four hours. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with water. The organic phase was extracted with dichloromethane, and then washed with water three times. After drying with anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure. Purification was performed by column chromatography using petroleum ether: dichloromethane = 6:1 (volume ratio) as an eluent to obtain compound 57-b about 1.36 g, yield: 76.0%. MS: 506.85.

[0193] Synthesis of compound 57-c:

[0194] Compound 57-b (1.32 g, 2.60 mmol), triethyl phosphite (20 mL) were added into a 50 mL three-necked flask under nitrogen atmosphere, and the reaction was stirred at 180 °C for 3 h. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with saturated aqueous ammonium chloride solution, extracted with dichloromethane, and the combined organic phase was washed with water for three times. After dried over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and then purified by column chromatography with petroleum ether: dichloromethane = 1:4 (volume ratio) as eluent to give compound 57-c about 0.89 g in 60.8% yield. MS: 563.42.

[0195] Synthesis of compound (57):

[0196] Compound 57-c (0.85 g, 1.50 mmol) was accurately weighed and dissolved in 20 mL of 1,4-dioxane, and then nitrogen was bubbled for 30 min. Trimethylsilyl bromide (0.85 mL) was added dropwise, and the reaction was stirred at 70 °C overnight. After the starting material was completely reacted, most of the solvent was removed by distillation under reduced pressure, and then quenched with water to precipitate a large amount of white solid. The solid was filtered and recrystallized from tetrahydrofuran to give compound (57) about 0.41 g in 53.9% yield. MALDI-TOF-MS: 507.28.

[0197] Synthesis Example 10: Synthesis of compound (63)

[0198]

[0199] Synthesis of compound 63-a:

[0200] 3,8-Dibromo-11,12-dihydroindolo[2,3-a]carbazole (2.48 g, 6 mmol), thiophen-2-ol (1.32 g, 13.2 mmol) were accurately weighed and dissolved in 30 mL of toluene, and then potassium phosphate (5.09 g, 24 mmol) and cuprous iodide (0.23 g, 1.2 mmol) were added. Nitrogen was bubbled for 30 min, and then the reaction was stirred at 110 °C overnight. After the starting material was completely reacted, the reaction solution was cooled to room temperature, and then quenched with water, extracted with dichloromethane, and the combined organic phase was washed with water for three times. After dried over anhydrous sodium sulfate, the excess solvent was removed by distillation under reduced pressure, and then purified by column chromatography with petroleum ether: dichloromethane = 4:1 (volume ratio) as eluent to give compound 63-a about 1.58 g in 58.2% yield. MS: 452.63.

[0201] Synthesis of compound 63-b:

[0202] Accurately weigh compound 63-a (1.55 g, 3.43 mmol) into a three-necked flask with 1,4-dibromobutane (40 mL), add tetrabutylammonium bromide (0.66 g, 2.06 mmol) and 50% potassium hydroxide aqueous solution (10 mL), and then pass nitrogen for 30 min. The reaction is carried out at 70 °C for 6 h. After the raw material is completely reacted, the reaction solution is cooled to room temperature, quenched with water, extracted with dichloromethane, and the organic phases are combined and washed with water three times. After drying over anhydrous sodium sulfate, the excess solvent is removed by distillation under reduced pressure, and column chromatography is performed for purification, using petroleum ether:dichloromethane = 12:1 (volume ratio) as the eluent, to obtain compound 63-b, about 1.61 g, yield: 64.9%. MS: 722.40.

[0203] Synthesis of compound 63-c:

[0204] Compound 63-b (1.59 g, 2.20 mmol) and triethyl phosphite (30 mL) are added to a 50 mL three-necked flask under a nitrogen atmosphere, and the reaction is carried out at 180 °C for 5 h. After the raw material is completely reacted, the reaction solution is cooled to room temperature, quenched with saturated ammonium chloride aqueous solution, extracted with dichloromethane, and the organic phases are combined and washed with water three times. After drying over anhydrous sodium sulfate, the excess solvent is removed by distillation under reduced pressure, and column chromatography is performed for purification, using petroleum ether:dichloromethane = 1:1 (volume ratio) as the eluent, to obtain compound 63-c, about 1.16 g, yield 63.0%. MS: 837.11.

[0205] Synthesis of compound (63):

[0206] Compound 63-c (1.09 g, 1.3 mmol) is accurately weighed and dissolved in 25 mL of 1,4-dioxane, nitrogen is passed for 30 min, and then trimethylsilyl bromide (1.09 mL) is added dropwise, and the reaction is carried out at 70 °C overnight. After the raw material is completely reacted, most of the solvent is removed by distillation under reduced pressure, and the reaction solution is quenched with water, and a large amount of white solid is precipitated. The solid is filtered, and recrystallized from tetrahydrofuran to obtain compound (63), about 0.54 g, yield 57.3%. MALDI-TOF-MS: 724.56.

[0207] Synthesis Example 11: Synthesis of compound (64)

[0208]

[0209] Synthesis of compound 64-a:

[0210] Accurately weigh 3,8-dibromo-11,12-dihydroindolo[2,3-a]carbazole (2.48 g, 6 mmol), phenol (1.24 g, 13.2 mmol) into 30 mL of toluene and stir to dissolve, then add potassium phosphate (5.09 g, 24 mmol) and cuprous iodide (0.23 g, 1.2 mmol), and stir at 110°C for 30 minutes. After the raw material is completely reacted, cool the reaction solution to room temperature, add water to quench, then extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography with petroleum ether:dichloromethane = 3:1 (volume ratio) as the eluent to obtain about 1.63 g of compound 64-a, with a yield of 61.7%. MS: 440.22.

[0211] Synthesis of compound 64-b:

[0212] Accurately weigh compound 64-a (1.62 g, 3.68 mmol) into a three-necked flask containing 1,3-dibromopropane (40 mL), then add tetrabutylammonium bromide (0.71 g, 2.21 mmol) and 50% potassium hydroxide aqueous solution (10 mL), and stir at 70°C for 6 hours. After the raw material is completely reacted, cool the reaction solution to room temperature, add water to quench, then extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography with petroleum ether:dichloromethane = 10:1 (volume ratio) as the eluent to obtain about 1.59 g of compound 64-b, with a yield of 63.3%. MS: 682.33.

[0213] Synthesis of compound 64-c:

[0214] Under a nitrogen atmosphere, add compound 64-b (1.57 g, 2.30 mmol) and triethyl phosphite (30 mL) into a 50 mL three-necked flask, and stir at 180°C for 5 hours. After the raw material is completely reacted, cool the reaction solution to room temperature, then add saturated ammonium chloride aqueous solution to quench, extract with dichloromethane, combine the organic phases, and wash with water three times. Dry over anhydrous sodium sulfate, then remove the excess solvent under reduced pressure, and purify by column chromatography with petroleum ether:dichloromethane = 1:2 (volume ratio) as the eluent to obtain about 1.15 g of compound 64-c, with a yield of 64.9%. MS: 796.94.

[0215] Synthesis of compound (64):

[0216] Compound 64-c (1.08 g, 1.40 mmol) was accurately weighed and dissolved in 25 mL of 1,4-dioxane. After purging with nitrogen for 30 minutes, trimethylbromosilane (1.08 mL) was added dropwise, and the mixture was heated to 70 °C and stirred overnight. After the starting material had completely reacted, most of the solvent was removed by vacuum distillation. After quenching with water, a large amount of white solid precipitated. The solid was filtered and recrystallized from tetrahydrofuran to give approximately 0.49 g of compound (64), with a yield of 51.1%. MALDI-TOF-MS: 684.67.

[0217] Organic photovoltaic (OPV) device fabrication examples

[0218] Device Example 1

[0219] Device structure such as Figure 1 As shown, the organic photovoltaic device includes a substrate, an anode, a hole transport layer, a photoactive layer, an electron transport layer, and a cathode stacked sequentially; wherein the materials of the anode, hole transport layer, photoactive layer, electron transport layer, and cathode are, in order: indium tin oxide (ITO) / SAM / photoactive layer material / PDINN / Ag.

[0220] Its preparation method includes the following steps:

[0221] 1) ITO substrate cleaning: Clean the ITO conductive glass with detergent, rinse it clean, and then ultrasonically clean it with deionized water, acetone, and isopropanol for 15 minutes. Then dry it with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0222] 2) Hole transport layer preparation: The hole transport material solution (the self-assembled small molecule material compound (3) is dissolved in ultra-dry ethanol with a concentration of 0.5 mg / mL) is uniformly spin-coated onto ITO in air at a speed of 3000 rpm for 30 s and dried at 100 °C for 5 min to obtain the hole transport layer.

[0223] 3) Preparation of photoactive layer

[0224] In a glove box (inert gas atmosphere), the photoactive layer material solution is uniformly spin-coated onto the hole transport layer at a speed of 1800-3000 rpm to obtain a photoactive layer with a total thickness of approximately 100 nm.

[0225] The preparation method of the photoactive layer material solution is: dissolving the donor material and the acceptor material in chloroform, and adding an additive 2,4,6-tribromopyrimidine to obtain a photoactive layer material solution. The donor material in the photoactive layer material solution is selected from polymer D18 and polymer PM6, and the acceptor material is selected from L8-BO; the mass ratio of polymer D18:PM6:L8-BO added to the chloroform solution is 0.8:0.2:1.2, the total concentration is 17.6 mg / mL, and the content of the additive 2,4,6-tribromopyrimidine is 50% of the total mass of D18, PM6 and L8-BO.

[0226] 4) Preparation of the electron transport layer

[0227] The device with the prepared photoactive layer is heat annealed on a hot stage at 80°C for 10 min, and then the electron transport layer material PDINN (PDINN is dissolved in methanol to prepare a solution with a concentration of 1.0 mg / mL) is uniformly spin-coated on the photoactive layer, the spin-coating speed is 3000 rpm, and the spin-coating time is 30 s, to obtain the electron transport layer.

[0228] 5) Preparation of the cathode layer

[0229] Ag is evaporated on the electron transport layer in a high vacuum (1×10 -6 millibar) to form a cathode layer with a thickness of about 100 nm.

[0230] 6) Packaging

[0231] The device is packaged with a UV-hardened curing resin in a nitrogen glove box.

[0232] Device examples 2-10

[0233] The preparation method of device examples 2-10 is the same as that of device example 1, and the difference lies in the selection of the self-assembled small molecule material in the hole transport layer. Specifically, the self-assembled small molecule material compound (3) is replaced by compound (6), compound (9), compound (21), compound (26), compound (35), compound (41), compound (46), compound (57), compound (63) and compound (64) respectively, and the specific details are shown in Table 1.

[0234] Device comparative examples 1-2

[0235] The preparation method of device comparative examples 1-2 is the same as that of device example 1, and the difference lies in the self-assembled small molecule material in the hole transport layer. Specifically, the self-assembled small molecule material compound (3) is replaced by compound (Ref-1) and compound (Ref-2) respectively, and the structures are as follows:

[0236]

[0237] The prepared organic photovoltaic devices were tested for performance. Under the irradiation of a solar simulator AM1.5 standard light, the device data were as shown in Table 1.

[0238] Table 1

[0239]

[0240] As can be seen from the data in Table 1, when the self-assembled small molecule material according to the present application is applied as a hole transport layer in an organic photovoltaic device, the device exhibits more excellent photoelectric conversion efficiency relative to the comparative device. In particular, the device examples 1, 2, 3, 10 and 11 exhibit photoelectric conversion efficiency of more than 20%. The reason is that, compared with the compound (Ref-1) and the compound (Ref-2), the self-assembled small molecule involved in the present application has better solubility and spatial configuration as well as hole transport performance.

[0241] Obviously, the above examples are merely illustrative and not intended to limit the embodiments. Based on the above description, other different forms of changes or variations can be made by those of ordinary skill in the art. Here, it is not necessary and impossible to exhaust all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A self-assembling small molecule material, characterized in that: The self-assembled small molecule material has any one of the structures as shown in general formula (I): (I) wherein: m is selected from 0 or 1; L1 is selected from an alkyl group having 1-10 carbon atoms, a substituted or unsubstituted aromatic group having 6-20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms; Ar1 is selected from a substituted or unsubstituted aromatic group having 6-20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms; Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 6-20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms; The "substituted or unsubstituted" defined groups are either not substituted, or substituted with one or more substituents R, each occurrence of which is independently selected from -D, halogen, cyano, nitro, an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, an alkylthio group having 1-10 carbon atoms, an aromatic group having 6-20 carbon atoms, a heteroaromatic group having 5-20 ring atoms, or a combination of one or at least two groups from the group consisting of L2 is selected from an alkyl group having 1-10 carbon atoms, an aromatic group having 6-20 carbon atoms, a heteroaromatic group having 5-20 ring atoms, or a combination of at least two of the groups; * represents a connecting site.

2. The self-assembling small molecule material of claim 1, wherein: The Ar1 is selected from any one of the following groups: wherein: Z is selected from O, S or Se; Y is selected from O, S, Se, CR2R3, or NR4; R1is independently selected at each occurrence from -H, -D, halogen, cyano, nitro, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, an alkylthio group having from 1 to 10 carbon atoms, an aromatic group having from 6 to 20 carbon atoms, a heteroaromatic group having from 5 to 20 ring atoms, or a combination of one or at least two of the foregoing groups. R2, R3, R4are each occurrence, independently selected from -H, -D, alkyl having from 1 to 10 carbon atoms, or ; # represents a fused site selected from a C atom.

3. The self-assembling small molecule material of claim 2, wherein: The self-assembled small molecule material has any one of the structures as shown in general formula (II-1)-(II-6): 。 4. The self-assembling small molecule material of claim 3, wherein: The Ar2, Ar3 are independently selected from any one of the following groups: wherein: W is independently selected from O, S or Se at each occurrence; R2 is independently selected from -D, halogen, cyano, nitro, an alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms, an alkylthio group having 1-6 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a combination of at least two of the groups at each occurrence; n1 is selected from 0, 1, 2, 3, 4 or 5; n2 is selected from 0, 1, 2 or 3; n3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n4 is selected from 0, 1, 2, 3 or 4.

5. The self-assembling small molecule material of claim 4, wherein: The general formula (II-1) is selected from any one of the following structures: 。 6. The self-assembling small molecule material of claim 4, wherein: The general formula (II-6) is selected from any one of the following structures: 。 7. The self-assembling small molecule material of any one of claims 1-6, wherein: said L1 is selected from , , , , , or .

8. The self-assembling small molecule material of claim 6, wherein: said L2 is selected from , , , , , or .

9. The self-assembling small molecule material of claim 1, wherein: The self-assembled small molecule material is selected from any one of the following structures: 。 10. An organic electronic device, said electronic device comprising a cathode, an anode, a photoactive layer located between the cathode and the anode, and a hole transport layer located between the anode and the photoactive layer, characterized in that: The hole transport layer material is selected from the self-assembled small molecule material according to any one of claims 1-9.

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