Organic compound and organic electronic device comprising same

Abstract

The invention relates to the field of organic solar cell materials, in particular to an organic compound and an organic electronic device containing the same. According to the organic compound disclosed by the invention, a saturated non-aromatic ring system is fused through a central core, and morphology aggregation of the compound in an active layer is effectively adjusted, so that the compound shows good photoelectric property when being applied to an organic solar cell as an acceptor material.

Description

Technical Field

[0001] The invention relates to the field of organic solar cell materials, in particular to an organic compound and an organic electronic device comprising the same. Background Art

[0002] As a third-generation new solar cell technology, organic solar cells have the advantages of low cost, light weight and flexibility. Since 1986, Dr. Qingyun Deng of Kodak has creatively processed an organic solar cell with a double-layer structure. The solar cell uses a derivative of tetracarboxyperylene (PV) as an acceptor and copper phthalocyanine (CuPc) as a donor. The double-layer film is used as the light-absorbing active layer, achieving a solar energy conversion efficiency of more than 1%, which has opened up a new research direction for the development of organic solar cell technology. Since then, with the continuous improvement of the photoelectric efficiency of organic solar cells, it has gradually become a research hotspot.

[0003] The working principle of organic solar cells is as follows: after absorbing photons, the photoactive layer donor and acceptor materials form electron-hole pairs with certain binding energy, i.e., photogenerated excitons; driven by the exciton concentration gradient, the photogenerated excitons diffuse to the interface between the donor and the acceptor and transform into CT state excitons with relatively weak binding energy; driven by the energy level difference, the CT state excitons overcome the binding energy and dissociate into carriers; the separated electrons and holes become freely movable carriers, where electrons move to the cathode and holes move to the anode. The cathode and anode capture the electrons and holes that move to the electrode vicinity and can output charges to the outside, thereby realizing energy supply. Therefore, the selection of the photoactive layer donor and acceptor materials is particularly critical.

[0004] The development of organic solar cell acceptor materials can be divided into three stages: the first stage is based on PCBM fullerene acceptor materials. Since PCBM was synthesized in 1995 and used in bulk heterojunction organic solar cells, fullerene acceptors have dominated organic photovoltaic acceptor materials for about 20 years, with PC 61 BM and PC 71Fullerenes and their derivatives, represented by BM, have dominated the electron acceptor materials due to their high electron affinity, isotropic electron transfer ability and high electron mobility. However, the limitations of the molecular structure of fullerene acceptors lead to weak absorption in the visible light region and poor energy level adjustability, which limits the efficiency improvement of organic solar cells. The second stage is the stage of non-fullerene acceptor materials based on ITIC structure. In 2015, Zhan Xiaowei and others first proposed the concept of condensed ring electron acceptors and synthesized ADA-type narrow-bandgap small molecule acceptor ITIC based on IDTT core and indenone IC end. The device blended with polymer donor material PTB7-Th achieved an efficiency of 6.8%, breaking the efficiency record of non-fullerene acceptor materials at that time. The third stage is the stage of non-fullerene acceptor materials based on Y6 structure. In 2017, Zou Yingping's research group at Central South University introduced electron-deficient units into the central core of condensed ring non-fullerene acceptors, and used this strategy to design and synthesize the first A-DA'DA-type narrow-bandgap small molecule acceptor BZIC. After that, they optimized the structure based on BZIC and obtained the narrow bandgap small molecule acceptor Y6. By using PM6 as a donor and Y6 as an acceptor, the efficiency of organic solar cells was greatly increased to 15.6%. Subsequently, based on the matching of Y6 and its derivative acceptors with a variety of wide bandgap polymer donors with appropriate energy levels, the energy conversion efficiency of organic solar cells was increased to more than 20%, which greatly promoted the development of organic solar cell technology.

[0005] However, the current development of organic solar cell technology focuses too much on the optimization of device structure, and less on the photoactive layer acceptor materials. Therefore, it is necessary to develop more types of acceptor materials to promote the technological development and industrialization of organic solar cells. Summary of the invention

[0006] The object of the present invention is to provide a novel organic compound, which can be used as a photoactive layer acceptor material in an organic solar cell device, thereby optimizing the photoelectric performance of the organic solar cell.

[0007] To achieve the purpose of the present invention, the technical solution is as follows:

[0008] The present invention relates to an organic compound having a structure as shown in the general formula (I):

[0009] (I)

[0010] in:

[0011] Each occurrence of X is independently selected from CR3R4, NR5, O or S;

[0012] Each occurrence of Y is independently selected from CR6R7, NR8, O or S;

[0013] Each occurrence of R3, R4, R5, R6, R7, and R8 is independently selected from -H, -D, -F, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups;

[0014] R1 and R2 are each independently selected from substituted or unsubstituted straight-chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkylthio having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0015] Each occurrence of M is independently selected from O or C(CN)2;

[0016] Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic groups having 5 to 20 ring atoms;

[0017] Ar3 and Ar4 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 to 20 ring atoms;

[0018] The “substituted or unsubstituted” means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups.

[0019] In a preferred embodiment, Ar3 and Ar4 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 to 8 ring atoms.

[0020] Furthermore, Ar3 and Ar4 are independently selected from any of the following groups:

[0021] ;

[0022] Wherein: Z, at each occurrence, is independently selected from O, S or Se;

[0023] R9, at each occurrence, is independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkylthio having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0024] # indicates a fusion site; * indicates a linking site.

[0025] Furthermore, the organic compound according to the present invention has a structure as shown in the general formula (II-1) or (II-2):

[0026]

[0027] Furthermore, the organic compound described in the general formula (II-1) is selected from any of the following general structures:

[0028] .

[0029] Furthermore, the organic compound described in general formula (II-2) is selected from any of the following general structures:

[0030] .

[0031] In one embodiment, each occurrence of Z in the general formula (II-1), general formula (II-2), and general formula (III-1) to (III-8) is independently selected from S or Se.

[0032] In one embodiment, each occurrence of R3 and R4 in the above formula is independently selected from -H, -D, -F or methyl.

[0033] In one embodiment, each occurrence of R5 is selected from -H, -F or methyl.

[0034] In one embodiment, each occurrence of R3 and R4 in the general formula (III-1) is identically selected from -H, -F or methyl.

[0035] In one embodiment, R3 and R4 in the general formula (III-2) are identically selected from -H, -F or methyl.

[0036] In one embodiment, R3 and R4 in the general formula (III-5) are identically selected from -H, -F or methyl.

[0037] In one embodiment, each occurrence of R3 and R4 in the general formula (III-7) is identically selected from -H, -F or methyl.

[0038] In one embodiment, in the general formula (III-5), R5 is selected from -H or methyl.

[0039] In one embodiment, R5 in the general formula (III-6) is selected from -H, -F or methyl.

[0040] In one embodiment, each occurrence of R6 and R7 is independently selected from -H, -D, -F or methyl.

[0041] In one embodiment, each occurrence of R8 is selected from -H, -F or methyl.

[0042] In a specific embodiment, the Select from any of the following structures:

[0043] ;

[0044] # indicates a fusion site.

[0045] In a specific embodiment, the Select from any of the following structures:

[0046] .

[0047] In a specific embodiment, the Select from any of the following structures:

[0048] .

[0049] In a specific embodiment, the general formula Select from any of the following structures:

[0050] .

[0051] In a specific embodiment, the Selected from or or .

[0052] In a specific embodiment, the Selected from or or .

[0053] In one embodiment, the Selected from , where * indicates the attachment site.

[0054] In a preferred embodiment, the Selected from .

[0055] In one embodiment, Ar1 and Ar2 are independently selected from * A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R * A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; said R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight-chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

[0056] Preferably, Ar1 and Ar2 are independently selected from the following groups:

[0057] ;

[0058] in,

[0059] Each occurrence of V is independently selected from N or CR 10 ;

[0060] Each occurrence of W is independently selected from O, S, and Se;

[0061] R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight-chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

[0062] Furthermore, the R 10 Each occurrence is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-6 carbon atoms, branched or cyclic alkyl having 3-6 carbon atoms, straight-chain alkoxy having 1-6 carbon atoms, branched or cyclic alkoxy having 3-6 carbon atoms, straight-chain alkylthio having 1-6 carbon atoms, branched or cyclic alkylthio having 3-6 carbon atoms.

[0063] Specifically, the and All are selected from any of the following groups, but not limited to:

[0064] .

[0065] In one embodiment, each occurrence of R1 and R2 is independently selected from a substituted or unsubstituted straight-chain alkyl group having 1-20 carbon atoms, a substituted or unsubstituted branched-chain alkyl group having 3-20 carbon atoms, a substituted or unsubstituted straight-chain alkoxy group having 1-20 carbon atoms, a substituted or unsubstituted branched-chain alkoxy group having 3-20 carbon atoms, a substituted or unsubstituted straight-chain alkylthio group having 1-20 carbon atoms, a substituted or unsubstituted branched-chain alkylthio group having 3-20 carbon atoms, a substituted or unsubstituted aromatic group having 6-10 carbon atoms, and a substituted or unsubstituted heteroaromatic group having 5-10 ring atoms.

[0066] In one embodiment, R1 and R2 are independently selected from , where R 11 Each occurrence is independently selected from a straight chain alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms; R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a cyclic alkyl group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups; r is selected from an integer greater than or equal to 0.

[0067] It should be noted that the maximum value that r can choose is R 11 The maximum number of substitutable sites in a group.

[0068] In one embodiment, r is selected from 0, 1, 2, 3 or 4.

[0069] In a specific embodiment, the R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, cyclohexyl, adamantyl, phenyl, phenyl substituted with one or more -F, phenyl substituted with one or more -Cl, thienyl, or pyridinyl.

[0070] Furthermore, in the organic compound, R1 and R2 are selected from the same group.

[0071] In a specific embodiment, R1 and R2 are selected from the following structures, but are not limited thereto:

[0072] , , .

[0073] In one embodiment, each occurrence of R9 is independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl having 1-20 carbon atoms, substituted or unsubstituted branched-chain alkyl having 3-20 carbon atoms, substituted or unsubstituted straight-chain alkoxy having 1-20 carbon atoms, substituted or unsubstituted branched-chain alkoxy having 3-20 carbon atoms, substituted or unsubstituted straight-chain alkylthio having 1-20 carbon atoms, substituted or unsubstituted branched-chain alkylthio having 3-20 carbon atoms, substituted or unsubstituted aromatic group having 6-20 carbon atoms, substituted or unsubstituted heteroaromatic group having 5-20 ring atoms.

[0074] Further, each occurrence of R9 is independently selected from -H, -D, or the following groups:

[0075] , ;

[0076] in:

[0077] R 12 Each occurrence is independently selected from the group consisting of straight chain alkyl having 1-20 carbon atoms, branched chain alkyl having 3-20 carbon atoms, straight chain alkoxy having 1-20 carbon atoms, branched chain alkoxy having 3-20 carbon atoms, straight chain alkylthio having 1-20 carbon atoms, branched chain alkylthio having 3-20 carbon atoms;

[0078] Ar5, at each occurrence, is independently selected from an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 5 to 20 ring atoms;

[0079] R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a cyclic alkyl group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups;

[0080] R bEach occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, cyclic alkylthio having 3-20 carbon atoms, or a group formed by a combination of the above groups;

[0081] m1 is selected from integers greater than or equal to 0; n is selected from integers greater than or equal to 0.

[0082] It should be noted that the maximum value that can be selected for m1 is the maximum number of substitutable sites in the Ar5 group; the maximum value that can be selected for n is R 12 The maximum number of substitutable sites in a group.

[0083] In a specific embodiment, the m1 is selected from 0, 1, 2, 3 or 4.

[0084] In one embodiment, n is selected from 0, 1, 2, 3 or 4.

[0085] In a specific embodiment, the R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, cyclohexyl, adamantyl, phenyl, thienyl, or pyridinyl.

[0086] In a specific embodiment, the R b Each occurrence is independently selected from a straight chain alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms.

[0087] In a specific embodiment, each occurrence of Ar5 is independently selected from phenyl, thienyl or pyridyl.

[0088] In a specific embodiment, R9 is selected from the following groups, but is not limited thereto:

[0089] -H, -D, -C7H 15 、-C9H 19 , -C 10 H 21 , -C 11 H 23 , -C 12 H 25、 -OC 10 H 21 、-OC 11 H 23 、-OC 12 H 25, -SC 10 H 21 , -SC 11 H 23 , -SC 12 H 25 , , , , , , , .

[0090] In a specific embodiment, the organic compound according to the present invention is selected from the following structures, but is not limited thereto:

[0091] .

[0092] The present invention further relates to a mixture comprising an organic compound as described above and at least one other organic functional material. Preferably, the other organic functional material is selected from a photoactive layer donor material and / or another photoactive layer acceptor material.

[0093] Further, the mixture comprises the organic compound as described above and at least one photoactive layer donor material. Preferably, the photoactive layer donor material is selected from a polymer donor material; further, the photoactive layer donor material can be selected from one, two or more of PBDB-T, PM6, PM7, D18, D18-Cl, PTO2, PB2, PB2F, PTVT-BT, PTQ10, PTQ11, PBQx-TCl, PQM-Cl, J106, J52-Cl, PCE10.

[0094] The present invention further relates to a composition comprising an organic compound or a mixture as described above, and at least one organic solvent.

[0095] Preferably, the organic solvent can be selected from the group consisting of dichloromethane, chloroform, chlorobenzene, chloroform, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,5-dimethyltetrahydrofuran, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decahydronaphthalene, indane, methyl benzoate, ethyl benzoate, mesitylene, or a mixture of two or more thereof.

[0096] Preferably, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0097] In one embodiment, the composition may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives may be selected from, but not limited to, 1,8-diiodooctane (DIO), diphenyl ether (DPE), anthracene, 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.

[0098] The present invention further relates to an organic electronic device, comprising a first electrode, a second electrode, and at least one functional layer located between the first electrode and the second electrode, wherein the at least one functional layer comprises an organic compound or a mixture as described above or is prepared from a composition. Preferably, the organic electronic device is selected from an organic photovoltaic cell (OPV), an organic light emitting diode (OLED), an organic field effect transistor (OFET), an organic laser, an organic photodetector (OPD), etc. Preferably, the organic electronic device is selected from an organic photovoltaic cell (OPV).

[0099] Furthermore, according to the present invention, the organic electronic device is selected from an organic photovoltaic cell, which comprises at least an anode, a cathode and a photoactive layer located between the anode and the cathode, and the photoactive layer comprises the organic compound or mixture as described above, or is prepared from the above composition.

[0100] At least one of the anode and cathode is transparent or translucent to facilitate the incidence of light. 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; 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 thereto.

[0101] The photoactive layer comprises a photoactive layer donor material and a photoactive layer acceptor material. The photoactive layer donor material is preferably selected from one, two or more of PBDB-T, PM6, PM7, D18, D18-Cl, PTO2, PB2, PB2F, PTVT-BT, PTQ10, PTQ11, PBQx-TCl, PQM-Cl, J106, J52-Cl, and PCE10, but is not limited thereto.

[0102] The photoactive layer acceptor material at least comprises the organic compound as described above; further, the photoactive layer acceptor material may further comprise another photoactive layer acceptor, preferably, the another photoactive layer acceptor material is selected from a non-fullerene acceptor material or a fullerene derivative acceptor material. Specifically, the another photoactive layer acceptor material is selected from one, two or more of PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), Y6, L8-BO, BTP-eC9, N3, H2, Z7, Z8, m-THE, and m-PEH, but is not limited thereto.

[0103] Furthermore, the photoactive layer can be prepared by the following method: dissolving the photoactive layer donor and acceptor material in an organic solvent to obtain a photoactive layer solution, and the solution is used to prepare the photoactive layer by a printing or coating method. The printing or coating method can be, but is not limited to, inkjet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slit extrusion coating, etc. The preferred methods are slit coating, spin coating and inkjet printing.

[0104] The mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:0.8~1:1.5; further, the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:1~1:1.5; the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:1~1:1.2.

[0105] The concentration of the photoactive layer donor material in the organic solvent is preferably 3-15 mg / mL; further, the concentration of the photoactive layer donor material in the organic solvent is preferably 4-10 mg / mL.

[0106] In one embodiment, the organic photovoltaic cell sequentially stacks an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer and a cathode from bottom to top, and the photoactive layer comprises the organic compound or mixture as described above, or is prepared from the above composition.

[0107] Preferably, the cathode buffer layer material can be selected from metal complexes, metal oxides, metal salts, etc. with low work function, such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it 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 to this.

[0108] The anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoO x ), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WO x , preferably, x is selected from 2 or 3), small molecule self-assembly materials such as 2PACz, MeO-2PACz, etc., but not limited thereto.

[0109] It should be noted that, in order to improve the performance of the organic photovoltaic cell device, the organic photovoltaic cell may further include other functional layers, including but not limited to a charge blocking layer and a charge transport layer.

[0110] Furthermore, the organic solar cell 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.

[0111] In one embodiment, as a substrate, a substrate having excellent transparency, surface smoothness, ease of handling, 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 may include a film in a single-layer or multi-layer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), polyparaxylene (Parylene), etc., but is not limited thereto, and a substrate commonly used for organic solar cells may also be used.

[0112] The organic solar cell described in the present invention is mainly used in wearable devices, smart Internet of Things, smart home, smart agriculture, building photovoltaics, new energy vehicles and other fields.

[0113] Compared with the prior art, the present invention has the following significant advantages: the present invention designs and synthesizes an ADA-type fused ring receptor material, which has a saturated non-aromatic ring system fused to the central core, effectively regulating the morphology aggregation of the compound in the active layer, so that the compound has a more ideal molecular stacking and phase separation size, so that the compound based on the present invention exhibits better exciton dissociation and charge transfer performance when used as a receptor material in an organic photovoltaic cell, thereby improving the photoelectric performance of the organic photovoltaic cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0114] Figure 1 It is a schematic structural diagram of a device embodiment of the present invention. DETAILED DESCRIPTION

[0115] In order to make the purpose, technical solution and effect of the present application clearer and more specific, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0116] The terms "and / or", "or / and", and "and / or" used in this article include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include 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 three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").

[0117] In the present invention, organic photovoltaic device, organic solar cell, OPV and OSC have the same meaning and can be interchangeable.

[0118] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0119] In the present invention, when a group contains multiple substituents with the same symbol, the substituents may be the same or different from each other. , the six Rs on the benzene ring may be the same or different from each other.

[0120] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0121] 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 a quinoline ring is 10, the number of ring atoms of a thienyl group is 5, and the number of ring atoms of a thienothiophene group is 8.

[0122] In the present invention, "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aromatic group (such as phenyl) or a polycyclic aromatic group. In other words, the aromatic group can be a monocyclic aromatic group, a condensed aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, monocyclic aromatic groups and condensed aromatic groups conjugated by carbon-carbon bonds, and two or more condensed aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated by carbon-carbon bonds can also be regarded as aromatic groups of the present application. Preferably, the aromatic group is selected from aromatic groups with 6-30 C atoms; further, selected from aromatic groups with 6-20 C atoms; further, selected from aromatic groups with 6-10 C atoms; aromatic groups include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, dinaphthylenyl, acenaphthene and derivatives thereof.

[0123] In the present invention, "heteroaromatic group" refers to a monovalent heteroaromatic ring or a derivative thereof containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatom may be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group may be a monocyclic heteroaromatic group or a polycyclic heteroaromatic group. In other words, the heteroaromatic group may be a single heteroaromatic ring system or a plurality of heteroaromatic ring systems conjugated by carbon-carbon bonds, and any heteroaromatic ring system is a heteroaromatic monocyclic ring or a heteroaromatic condensed ring. Preferably, the heteroaromatic group is selected from heteroaromatic groups having 5-30 ring atoms; further, selected from heteroaromatic groups having 5-20 ring atoms; further, selected from heteroaromatic groups having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to, thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.

[0124] In the present invention, the number of carbon atoms of the linear alkyl group may be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6. The number of carbon atoms of the branched alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. The number of carbon atoms of the cyclic alkyl group may be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of the linear alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, -C 10 H 21 , -C 11 H 23 , -C 12 H 25 , -C 13 H 27 , -C 14 H 29 , -C 15 H 31 , -C 16 H 33 Non-limiting examples of branched alkyl groups include isopropyl, branched alkyl groups containing 4 C atoms, branched alkyl groups containing 5 C atoms, branched alkyl groups containing 6 C atoms, branched alkyl groups containing 7 C atoms, branched alkyl groups containing 8 C atoms, branched alkyl groups containing 9 C atoms, branched alkyl groups containing 10 C atoms, branched alkyl groups containing 11 C atoms, branched alkyl groups containing 12 C atoms, branched alkyl groups containing 13 C atoms, branched alkyl groups containing 14 C atoms, branched alkyl groups containing 15 C atoms, and branched alkyl groups containing 16 C atoms. Non-limiting examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclic alkyl groups containing 7 C atoms, cyclic alkyl groups containing 8 C atoms, cyclic alkyl groups containing 9 C atoms, cyclic alkyl groups containing 10 C atoms (such as adamantyl), cyclic alkyl groups containing 11 C atoms, cyclic alkyl groups containing 12 C atoms, cyclic alkyl groups containing 13 C atoms, cyclic alkyl groups containing 14 C atoms, cyclic alkyl groups containing 15 C atoms, and cyclic alkyl groups containing 16 C atoms.

[0125] The term "alkoxy" refers to a group with the structure "-O-alkyl", i.e., an alkyl group as defined above connected to another group via an oxygen atom. The straight-chain alkoxy group means that the alkyl group in the "-O-alkyl" is selected from a straight-chain alkyl group, wherein the carbon number of the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy group means that the alkyl group in the "-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, or 3 to 6.

[0126] 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, or 1 to 6; 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, or 3 to 6.

[0127] In the present invention, when a linking site is not specified in a group, it means that any linking site in the group can be used as the linking site.

[0128] In the present invention, one or more groups "independently selected from" means that when one or more groups appear simultaneously and in multiple places in a compound, they are all independently selected and may be the same or different.

[0129] In the present invention, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.

[0130] In the process of describing the structural elements of the present invention, the words "include" or "comprises" and the like used in the present invention mean that the devices or materials appearing before the word include the devices or materials listed after the word and their equivalents, but do not exclude other devices or materials.

[0131] 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.

[0132] The "combinations thereof", "any combinations thereof", "any combinations thereof", "combinations" and the like used in the present invention include all suitable combinations of any two, any three or more items in the listed groups.

[0133] 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.

[0134] 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.

[0135] Organic Compound Synthesis Examples

[0136] Synthesis Example 1: Synthesis of Compound (2)

[0137]

[0138] Synthesis of compound 2-2:

[0139] Accurately weigh 100 mL of trifluoromethanesulfonic acid and add it to a 250 mL three-necked flask. Cool down to below 0 ° C under nitrogen protection, slowly add 4.7 mL of concentrated nitric acid (68%), and then slowly add compound 2-1 (10.4 g, 30 mmol) to the solution. After half an hour of reaction, the mass spectrometer monitors that the raw material is basically reacted completely, and it is a product of a single nitro group. Then the temperature is lowered to below 0 ° C again, and 4.7 mL of nitric acid is slowly added dropwise to precipitate solids. The temperature is raised to 80 ° C. After reacting for 12 hours, TLC and mass spectrometry monitor that the reaction is complete. After the reaction is cooled to room temperature, slowly pour it into 2.5 L of ice water, stirring while pouring, precipitate solids, filter, and obtain a crude product. Recrystallize it with ethanol to obtain about 11.32 g of compound 2-2. Yield: 86.6%. MS: 435.78

[0140] Synthesis of compound 2-4:

[0141] Accurately weigh compound 2-2 (8.7g, 20mmol), compound 2-3 (25.2g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The entire reaction system is heated to reflux and reacted for 4h. Remove the excess solvent by vacuum distillation, use petroleum ether: chloroform = 1:2 (volume ratio) as eluent, separate with silica gel chromatography column, and obtain about 16.19g of compound 2-4, with a yield of 84.5%. MS: 957.81.

[0142] Synthesis of compound 2-5:

[0143] Accurately weigh compound 2-4 (11.5 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 2-5 without further purification.

[0144] Synthesis of compound 2-6:

[0145] Add crude compound 2-5, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL into a 250 mL three-necked flask, heat to 85 ° C under nitrogen protection for 0.5 h, then add isooctane bromide (23.2 g, 120 mmol) and stir overnight. After cooling to room temperature, add water and extract with DCM, add anhydrous magnesium sulfate to dry the organic phase, filter, concentrate, add silica gel to the solid and mix with column chromatography, the eluent is PE: DCM = 5:1 (volume ratio), and obtain about 7.18 g of compound 2-6, with a two-step yield of 53.5%. MALDI-TOF-MS: 1117.74

[0146] Synthesis of compound 2-7:

[0147] Accurately weigh compound 2-6 (2.2 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:DCM=5:1 (volume ratio), and about 1.72 g of compound 2-7 was obtained, with a yield of 73.2%. MALDI-TOF-MS: 1174.12.

[0148] Synthesis of compound (2):

[0149] Accurately weigh compound 2-7 (1.2 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in turn, add 20 mL of anhydrous chloroform, heat to 60 ° C and stir for 12 hours under nitrogen protection. After the reaction solution cools down, remove the excess solvent by vacuum distillation, add silica gel to mix the sample and perform column chromatography, the eluent is PE:DCM=1:1 (volume ratio), and obtain about 861 mg of compound (2), with a yield of 53.9%. MALDI-TOF-MS: 1597.64.

[0150] Synthesis Example 2: Synthesis of Compound (4)

[0151]

[0152] Synthesis of compound 4-2:

[0153] Accurately weigh compound 2-2 (8.7g, 20mmol), compound 4-1 (23.9g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), and add them into a 500mL three-necked flask in sequence. Add 250mL of anhydrous toluene and replace nitrogen three times. The subsequent synthesis steps refer to the synthesis of compound 2-4 to obtain about 12.81g of compound 4-2, with a yield of 71.8%. MS: 892.15.

[0154] Synthesis of compound 4-3:

[0155] Accurately weigh compound 4-2 (10.7 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 4-3 without further purification.

[0156] Synthesis of compound 4-4:

[0157] Add crude compound 4-3, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL into a 250 mL three-necked flask, and heat to 85 ° C for 0.5 h under nitrogen protection, then add isooctane bromide (23.2 g, 120 mmol) and stir overnight. After cooling to room temperature, add water to cool the reaction mixture, extract the organic phase with DCM, add anhydrous magnesium sulfate to dry, filter, concentrate, add silica gel to the solid, and perform column chromatography. The eluent is PE: EA = 15:1 (volume ratio). About 5.64 g of compound 4-4 is obtained, and the two-step yield is 44.7%. MALDI-TOF-MS: 1051.71

[0158] Synthesis of compound 4-5:

[0159] Accurately weigh compound 4-4 (2.1 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=10:1 (volume ratio), and about 1.78 g of compound 4-5 was obtained, with a yield of 80.4%. MALDI-TOF-MS: 1107.38.

[0160] Synthesis of compound (4):

[0161] Accurately weigh compound 4-5 (1.1 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, and add 20 mL of anhydrous chloroform. The subsequent synthesis steps refer to the synthesis of compound (2) to obtain about 994 mg of compound (4), with a yield of 64.9%. MALDI-TOF-MS: 1532.67.

[0162] Synthesis Example 3: Synthesis of Compound (10)

[0163]

[0164] Synthesis of compound 10-3:

[0165] Accurately weigh compound 10-1 (71.8g, 200mmol), compound 10-2 (43.8g, 200mmol), Pd(PPh3)4 (2.3g, 2mmol), add them into a 1L three-necked flask, add 500mL of anhydrous toluene, and replace nitrogen three times. Heat and reflux for 4h, remove excess solvent by vacuum distillation, use PE:DCM=10:1 (volume ratio) as eluent, separate with silica gel chromatography column, and obtain about 60.10g of compound 10-3, with a yield of 89.6%. MS: 335.21.

[0166] Synthesis of compound 10-4:

[0167] Accurately weigh compound 10-3 (25.1g, 75mmol) into a 1L three-necked flask, add 500mL dry tetrahydrofuran, and replace nitrogen three times. Lower the temperature of the entire system to -78°C, slowly add 45mL of 2.5mol / L n-butyl lithium, maintain -70°C for half an hour, add tributyltin chloride (48.8g, 150mmol), maintain -70°C for 2h, and monitor the reaction by TLC and mass spectrometry. Quench with water, extract with EA, and remove the solvent by vacuum distillation to obtain about 32.45g of compound 10-4 with a yield of 69.4%. MS: 623.53.

[0168] Synthesis of compound 10-5:

[0169] Accurately weigh compound 2-2 (8.7g, 20mmol), compound 10-4 (24.9g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), and add them to a 500mL three-necked flask in sequence. Add 250mL of anhydrous toluene and replace nitrogen three times. The subsequent synthesis steps refer to the synthesis of compound 2-4 to obtain about 16.67g of compound 10-5 with a yield of 88.3%. MS: 944.16.

[0170] Synthesis of compound 10-6:

[0171] Accurately weigh compound 10-5 (11.3 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 10-6 without further purification.

[0172] Synthesis of compound 10-7:

[0173] The crude compound 10-6, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL were added to a 250 mL three-necked flask. Under nitrogen protection, the mixture was heated to 85 °C for 0.5 h, and then 2-butyl-1-bromooctane (29.9 g, 120 mmol) was added and stirred overnight. After cooling to room temperature, water was added and extracted with DCM. The organic phase was dried with anhydrous magnesium sulfate, filtered, concentrated, and the solid was added with silica gel column chromatography. The eluent was PE:DCM=8:1 (volume ratio). About 9.18 g of compound 10-7 was obtained, and the two-step yield was 62.9%. MALDI-TOF-MS: 1216.21

[0174] Synthesis of compound 10-8:

[0175] Accurately weigh compound 10-7 (2.4 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=10:1 (volume ratio), and about 1.52 g of compound 10-8 was obtained, with a yield of 59.8%. MALDI-TOF-MS: 1271.49.

[0176] Synthesis of compound (10):

[0177] Accurately weigh compound 10-8 (1.3 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, and add 20 mL of anhydrous chloroform. The subsequent synthesis steps refer to the synthesis of compound (2) to obtain about 945 mg of compound (10), with a yield of 55.7%. MALDI-TOF-MS: 1696.15.

[0178] Synthesis Example 4: Synthesis of Compound (12)

[0179]

[0180] Synthesis of compound 12-2:

[0181] Accurately weigh compound 12-1 (48.7g, 150mmol) into a 1L three-necked flask, add 500mL dry tetrahydrofuran, and replace nitrogen three times. Lower the temperature of the entire system to -78°C, slowly add 66mL of 2.5mol / L n-butyl lithium, maintain -70°C for half an hour, add trimethylsilyl chloride (19.4g, 180mmol), maintain -70°C for 2h, and monitor the reaction by TLC and mass spectrometry. Quench with water, extract with EA, remove the solvent by vacuum distillation, use PE:DCM=10:1 (volume ratio) as eluent, separate with a silica gel chromatography column, and obtain about 33.84g of compound 12-2 with a yield of 56.8%. MS: 397.41.

[0182] Synthesis of compound 12-3:

[0183] Accurately weigh compound 12-2 (29.8g, 75mmol) into a 1L three-necked flask, add 500mL dry tetrahydrofuran, and replace nitrogen three times. Lower the temperature of the entire system to -78°C, slowly add 45mL of 2.5mol / L n-butyl lithium, maintain -70°C for half an hour, add tributyltin chloride (48.8g, 150mmol), maintain -70°C for 2h, and monitor the reaction by TLC and mass spectrometry. Quench with water, extract with EA, and remove the solvent by vacuum distillation to obtain about 38.41g of compound 12-3, with a yield of 74.6%. MS: 686.19.

[0184] Synthesis of compound 12-4:

[0185] Accurately weigh compound 2-2 (8.7g, 20mmol), compound 12-3 (27.4g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), and add them to a 500mL three-necked flask in sequence. Add 250mL of anhydrous toluene and replace nitrogen three times. The subsequent synthesis steps refer to the synthesis of compound 2-4 to obtain about 19.35g of compound 12-4 with a yield of 90.6%. MALDI-TOF-MS: 1067.98.

[0186] Synthesis of compound 12-5:

[0187] Accurately weigh compound 12-4 (12.8 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Under nitrogen protection, heat to 180 °C and stir overnight. Remove the solvent to obtain the crude compound 12-5 without further purification.

[0188] Synthesis of compound 12-6:

[0189] The crude compound 12-5, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL were added to a 250 mL three-necked flask, heated to 85 ° C for 0.5 h under nitrogen protection, and then bromoisooctane (23.2 g, 120 mmol) was added and stirred overnight. After cooling to room temperature, water was added to cool the reaction mixture, and the organic phase was extracted with DCM and dried with anhydrous magnesium sulfate, filtered, concentrated, and the solid was added to silica gel column chromatography, and the eluent was PE: EA = 8:1 (volume ratio), to obtain about 10.19 g of compound 12-6, with a yield of 69.1%. MALDI-TOF-MS: 1228.59

[0190] Synthesis of compound 12-7:

[0191] Compound 12-6 (8.6 g, 7 mmol), 50 mL of trifluoroacetic acid, and 200 mL of dichloromethane were added to a 500 mL three-necked flask and stirred overnight at room temperature under nitrogen protection. Saturated salt and EA were added to extract the liquid, anhydrous magnesium sulfate was added to the organic phase for drying, filtration, concentration, and the solid was added to silica gel column chromatography, the eluent was PE:DCM = 10:1 (volume ratio), and about 5.90 g of compound 12-7 was obtained, with a yield of 77.7%. MALDI-TOF-MS: 1084.23

[0192] Synthesis of compound 12-8:

[0193] Accurately weigh compound 12-7 (2.2 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=6:1 (volume ratio), and about 1.32 g of compound 12-8 was obtained, with a yield of 59.0%. MALDI-TOF-MS: 1139.34.

[0194] Synthesis of compound (12):

[0195] Accurately weigh compound 12-8 (1.1 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, and add 20 mL of anhydrous chloroform. The subsequent synthesis steps refer to the synthesis of compound (2) to obtain about 871 mg of compound (12), with a yield of 55.7%. MALDI-TOF-MS: 1564.35.

[0196] Synthesis Example 5: Synthesis of Compound (14)

[0197]

[0198] Synthesis of compound 14-2:

[0199] Accurately weigh 100 mL of trifluoromethanesulfonic acid and add it to a 250 mL three-necked flask. Cool down to below 0°C under nitrogen protection, slowly add 4.7 mL of concentrated nitric acid (68%), and then slowly add compound 14-1 (8.7 g, 30 mmol) to the solution. After half an hour of reaction, the mass spectrometer monitors that the raw material is basically reacted completely, and it is a product of a single nitro group. Then the temperature is lowered to below 0°C again, and 4.7 mL of nitric acid is slowly added dropwise to precipitate solids. The temperature is raised to 80°C. After reacting for 12 hours, TLC and mass spectrometry monitor that the reaction is complete. After the reaction is cooled to room temperature, slowly pour it into 2.5 L of ice water, stirring while pouring, a large amount of solids precipitate, and filter to obtain a crude product. Recrystallize it with ethanol to obtain about 8.55 g of compound 14-2, with a yield of 74.6%. MS: 382.11

[0200] Synthesis of compound 14-4:

[0201] Accurately weigh compound 14-2 (7.6g, 20mmol), compound 14-3 (18.3g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The entire reaction system is heated to reflux and reacted for 4h. Remove the excess solvent by vacuum distillation, use petroleum ether: chloroform = 1:2 (volume ratio) as eluent, separate with silica gel chromatography column, and obtain about 12.83g of compound 14-4, with a yield of 79.3%. MS: 808.69.

[0202] Synthesis of compound 14-5:

[0203] Accurately weigh compound 14-4 (9.7 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 14-5 without further purification.

[0204] Synthesis of compound 14-6:

[0205] Add crude compound 14-5, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL into a 250 mL three-necked flask, heat to 85 ° C under nitrogen protection for 0.5 h, then add isooctane bromide (23.2 g, 120 mmol) and stir overnight. After cooling to room temperature, add water and extract with DCM, add anhydrous magnesium sulfate to dry the organic phase, filter, concentrate, add silica gel to the solid and mix with column chromatography, the eluent is PE: DCM = 8:1 (volume ratio), and obtain about 6.47 g of compound 14-6, with a two-step yield of 55.6%. MS: 970.32

[0206] Synthesis of compound 14-7:

[0207] Accurately weigh compound 14-6 (1.9 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=6:1 (volume ratio), and about 1.63 g of compound 14-7 was obtained, with a yield of 79.5%. MALDI-TOF-MS: 1025.58.

[0208] Synthesis of compound (14):

[0209] Accurately weigh compound 14-7 (1.0 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, and add 20 mL of anhydrous chloroform. The subsequent synthesis steps refer to the synthesis of compound (2) to obtain about 618 mg of compound (14), with a yield of 42.6%. MALDI-TOF-MS: 1449.46.

[0210] Synthesis Example 6: Synthesis of Compound (25)

[0211]

[0212] Synthesis of compound 25-2:

[0213] Accurately weigh 100 mL of trifluoromethanesulfonic acid and add it to a 250 mL three-necked flask. Cool down to below 0 °C under nitrogen protection, slowly add 4.7 mL of concentrated nitric acid (68%), and then slowly add compound 25-1 (8.8 g, 30 mmol) to the solution. After half an hour of reaction, the mass spectrometer monitors that the raw material is basically reacted completely, and it is a product of a single nitro group. Then the temperature is lowered to below 0 °C again, and 4.7 mL of nitric acid is slowly added dropwise to precipitate solids. The temperature is raised to 80 °C. After reacting for 12 hours, TLC and mass spectrometry monitor that the reaction is complete. After the reaction is cooled to room temperature, slowly pour it into 2.5 L of ice water, stirring while pouring, a large amount of solids precipitate, filter, and obtain a crude product. Recrystallize it with ethanol to obtain 10.22 g of solids. Yield: 88.6%. MS: 384.67

[0214] Synthesis of compound 25-3:

[0215] Accurately weigh compound 25-2 (7.7g, 20mmol), compound 4-1 (23.9g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The entire reaction system is heated to reflux and reacted for 4h. Excess solvent is removed by vacuum distillation, and petroleum ether: chloroform = 5:1 (volume ratio) is used as eluent. Separate with a silica gel chromatography column to obtain about 15.52g of compound 25-3, with a yield of 92.4%. MS: 839.58.

[0216] Synthesis of compound 25-4:

[0217] Accurately weigh compound 25-3 (10 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 25-4 without further purification.

[0218] Synthesis of compound 25-5:

[0219] Add crude compound 25-4, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL into a 250 mL three-necked flask, heat to 85 ° C under nitrogen protection for 0.5 h, then add isooctane bromide (23.2 g, 120 mmol) and stir overnight. After cooling to room temperature, add water and extract with DCM, add anhydrous magnesium sulfate to dry the organic phase, filter, concentrate, add silica gel to the solid and mix with column chromatography, the eluent is PE: EA = 15: 1 (volume ratio), and obtain about 5.37 g of compound 25-5, with a yield of 44.8%. MS: 999.27

[0220] Synthesis of compound 25-6:

[0221] Accurately weigh compound 25-5 (2g, 2mmol) and add it to a 25mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0℃, and phosphorus oxychloride (0.6g, 4mmol) was weighed and slowly added dropwise to the reaction system. After the addition was completed, it was kept at 0℃ and stirred for 3h, and then naturally warmed to room temperature and reacted for 6h. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=6:1 (volume ratio), and about 1.36g of compound 25-6 was obtained, with a yield of 64.4%. MALDI-TOF-MS: 1055.38.

[0222] Synthesis of compound (25):

[0223] Accurately weigh compound 25-6 (1.1 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, and add 20 mL of anhydrous chloroform. The subsequent synthesis steps refer to the synthesis of compound (2) to obtain about 783 mg of compound (25), with a yield of 52.9%. MALDI-TOF-MS: 1480.45.

[0224] Synthesis Example 7: Synthesis of Compound (27)

[0225]

[0226] Synthesis of compound 27-2:

[0227] Accurately weigh compound 25-2 (7.7g, 20mmol), compound 27-1 (22.2g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The entire reaction system is heated to reflux and reacted for 4h. The subsequent synthesis steps refer to the synthesis steps of compound 25-3 to obtain about 13.27g of compound 27-2, with a yield of 87.8%. MS: 755.37.

[0228] Synthesis of compound 27-3:

[0229] Accurately weigh compound 27-2 (9.1 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 27-3 without further purification.

[0230] Synthesis of compound 27-4:

[0231] The crude compound 27-3, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL were added to a 250 mL three-necked flask. Under nitrogen protection, the mixture was heated to 85 °C for 0.5 h, and then 2-butyl-1-bromooctane (29.9 g, 120 mmol) was added and stirred overnight. After cooling to room temperature, water was added and extracted with DCM. The organic phase was dried with anhydrous magnesium sulfate, filtered, concentrated, and the solid was added with silica gel for column chromatography. The eluent was PE:DCM=2:1 (volume ratio). About 4.98 g of compound 27-4 was obtained, with a yield of 40.4%. MALDI-TOF-MS: 1027.45

[0232] Synthesis of compound 27-5:

[0233] Accurately weigh compound 27-4 (2g, 2mmol) and add it to a 25mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0℃, and phosphorus oxychloride (0.6g, 4mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was kept at 0℃ and stirred for 3h, and then naturally warmed to room temperature for 6h. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=10:1 (volume ratio), and about 1.65g of compound 27-5 was obtained, with a yield of 76.1%. MALDI-TOF-MS: 1083.78.

[0234] Synthesis of compound (27):

[0235] Accurately weigh compound 27-5 (1.1 g, 1 mmol), compound 27-6 (1.1 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, add 20 mL of anhydrous chloroform, and follow the subsequent synthesis steps as described for compound (2) to obtain about 694 mg of compound (27) with a yield of 44.1%. MALDI-TOF-MS: 1573.45.

[0236] Synthesis Example 8: Synthesis of Compound (29)

[0237]

[0238] Synthesis of compound 29-1:

[0239] Accurately weigh compound 25-2 (7.7g, 20mmol), compound 14-3 (18.3g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The entire reaction system is heated to reflux and reacted for 4h. The subsequent synthesis steps refer to the synthesis of compound 25-3 to obtain about 12.20g of compound 29-1, with a yield of 75.2%. MS: 811.53.

[0240] Synthesis of compound 29-2:

[0241] Accurately weigh compound 29-1 (9.7 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 29-2 without further purification.

[0242] Synthesis of compound 29-3:

[0243] Add crude compound 29-2, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL into a 250 mL three-necked flask, heat to 85 ° C under nitrogen protection for 0.5 h, then add isooctane bromide (23.2 g, 120 mmol) and stir overnight. After cooling to room temperature, add water and extract with DCM, add anhydrous magnesium sulfate to dry the organic phase, filter, concentrate, add silica gel to the solid and mix with column chromatography, the eluent is PE: DCM = 15: 1 (volume ratio), and obtain about 5.29 g of compound 29-3, with a yield of 45.3%. MS: 971.96

[0244] Synthesis of compound 29-4:

[0245] Accurately weigh compound 29-3 (1.9 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, and phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added to the sample column for chromatography, and the eluent was PE:DCM=8:1 (volume ratio), and about 1.66 g of compound 29-4 was obtained, with a yield of 80.7%. MS: 1028.05.

[0246] Synthesis of compound (29):

[0247] Accurately weigh compound 29-4 (1 g, 1 mmol), compound 29-5 (1.1 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, add 20 mL of anhydrous chloroform, and follow the subsequent synthesis steps as described for compound (2) to obtain about 821 mg of compound (29) with a yield of 52.9%. MALDI-TOF-MS: 1552.27.

[0248] Synthesis Example 9: Synthesis of Compound (32)

[0249]

[0250] Synthesis of compound 32-2:

[0251] Accurately weigh compound 25-2 (7.7g, 20mmol), compound 32-1 (24.7g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The entire reaction system is heated to reflux and reacted for 4h. The subsequent synthesis steps refer to the synthesis of compound 25-3 to obtain about 12.34g of compound 32-2, with a yield of 70.1%. MS: 879.56.

[0252] Synthesis of compound 32-3:

[0253] Accurately weigh compound 32-2 (10.5 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 32-3 without further purification.

[0254] Synthesis of compound 32-4:

[0255] The crude compound 32-3, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL were added to a 250 mL three-necked flask, heated to 85 ° C for 0.5 h under nitrogen protection, and then 2-butyl-1-bromooctane (29.9 g, 120 mmol) was added and stirred overnight. After cooling to room temperature, water was added to cool the reaction mixture, and the organic phase was extracted with DCM and dried with anhydrous magnesium sulfate, filtered, concentrated, and the solid was added to silica gel for column chromatography. The eluent was PE: EA = 2: 1 (volume ratio), and about 6.48 g of compound 32-4 was obtained, with a yield of 46.9%. MALDI-TOF-MS: 1151.39

[0256] Synthesis of compound 32-5:

[0257] Accurately weigh compound 32-4 (2.3 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=4:1 (volume ratio), and about 1.57 g of compound 32-5 was obtained, with a yield of 65.0%. MALDI-TOF-MS: 1208.59.

[0258] Synthesis of compound (32):

[0259] Accurately weigh compound 32-5 (1.2 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, add 20 mL of anhydrous chloroform, and follow the subsequent synthesis steps as described for compound (2) to obtain about 777 mg of compound (32) with a yield of 47.6%. MALDI-TOF-MS: 1632.53.

[0260] Synthesis Example 10: Synthesis of Compound (43)

[0261]

[0262] Synthesis of compound 43-2:

[0263] Accurately weigh compound 43-1 (23.4 g, 80 mmol), iodomethane (24.8 g, 176 mmol) and sodium hydroxide (12.8 g, 320 mmol) and add them to a 500 mL three-necked flask in sequence, add 250 mL DMF, replace nitrogen three times, stir at room temperature for 8 h, pour the reaction solution into water to precipitate solid, add silica gel to the solid and perform column chromatography, eluent PE:DCM=2:1 (volume ratio) to obtain about 10.75 g of compound 43-2, yield: 42.1%. MS: 319.29.

[0264] Synthesis of compound 43-3:

[0265] Accurately weigh 100 mL of trifluoromethanesulfonic acid and add it to a 250 mL three-necked flask. Cool down to below 0 °C under nitrogen protection, slowly add 4.7 mL of concentrated nitric acid (68%), and then slowly add compound 43-2 (9.6 g, 30 mmol) to the solution. After half an hour of reaction, the mass spectrometer monitors that the raw material is basically reacted completely, and it is a product of a single nitro group. Then the temperature is lowered to below 0 °C again, and 4.7 mL of nitric acid is slowly added dropwise to precipitate solids. The temperature is raised to 80 °C. After reacting for 12 hours, TLC and mass spectrometry monitor that the reaction is complete. After the reaction is cooled to room temperature, slowly pour it into 2.5 L of ice water, stirring while pouring, a large amount of solids precipitate, filter, and obtain a crude product. Recrystallize it with ethanol to obtain 9.23 g of solids. Yield: 74.9%. MS: 410.83

[0266] Synthesis of compound 43-4:

[0267] Accurately weigh compound 43-3 (8.2g, 20mmol), compound 4-1 (23.9g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), and add them into a 500mL three-necked flask in sequence. Add 250mL of anhydrous toluene and replace nitrogen three times. The subsequent synthesis steps refer to the synthesis of compound 2-4 to obtain about 14.60g of compound 43-4, with a yield of 84.3%. MS: 865.91.

[0268] Synthesis of compound 43-5:

[0269] Accurately weigh compound 43-4 (10.4 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 43-5 without further purification.

[0270] Synthesis of compound 43-6:

[0271] Add crude compound 43-5, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL into a 250 mL three-necked flask, heat to 85 ° C under nitrogen protection, react for 0.5 h, then add isooctane bromide (23.2 g, 120 mmol) and stir overnight. After cooling to room temperature, add water and extract with DCM, add anhydrous magnesium sulfate to dry the organic phase, filter, concentrate, add silica gel to the solid and mix with column chromatography, the eluent is PE: DCM = 1:1 (volume ratio), and obtain about 4.53 g of compound 43-6, with a yield of 36.8%. MS: 1025.21

[0272] Synthesis of compound 43-7:

[0273] Accurately weigh compound 43-6 (2.1 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added to the reaction system. After the addition was completed, it was stirred at 0°C for 3 hours, and then naturally warmed to room temperature for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added for column chromatography, and the eluent was PE:EA=1:1 (volume ratio), and about 1.36 g of compound 43-7 was obtained, with a yield of 62.9%. MALDI-TOF-MS: 1080.93.

[0274] Synthesis of compound 43:

[0275] Accurately weigh compound 43-7 (1.1 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, add 20 mL of anhydrous chloroform, and follow the subsequent synthesis steps as described for compound (2) to obtain about 917 mg of compound (43) with a yield of 60.9%. MALDI-TOF-MS: 1506.59.

[0276] Synthesis Example 11: Synthesis of Compound (54)

[0277]

[0278] Synthesis of compound (54):

[0279] Accurately weigh compound 12-8 (1.1 g, 1 mmol), compound 54-1 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, add 20 mL of anhydrous chloroform, and follow the subsequent synthesis steps as described for compound (2) to obtain about 741 mg of compound (54), with a yield of 47.1%. MALDI-TOF-MS: 1573.25.

[0280] Synthesis Example 12: Synthesis of Compound (58)

[0281]

[0282] Synthesis of compound 58-2:

[0283] Accurately weigh compound 2-2 (8.7g, 20mmol), compound 58-1 (13.2g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The specific synthesis steps refer to the synthesis of compound 2-4, and about 9.13g of compound 58-2 is obtained, with a yield of 74.8%. MS: 610.26.

[0284] Synthesis of compound 58-3:

[0285] Accurately weigh compound 58-2 (7.3 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 58-3 without further purification.

[0286] Synthesis of compound 58-4:

[0287] Add crude compound 58-3, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL into a 250 mL three-necked flask, heat to 85 ° C under nitrogen protection, react for 0.5 h, then add isooctane bromide (23.2 g, 120 mmol) and stir overnight. After cooling to room temperature, add water and extract with DCM, add anhydrous magnesium sulfate to dry the organic phase, filter, concentrate, add silica gel to the solid and mix with column chromatography, the eluent is PE: EA = 10: 1 (volume ratio), and obtain about 4.69 g of compound 58-4, with a yield of 50.7%. MS: 771.22

[0288] Synthesis of compound 58-5:

[0289] Accurately weigh compound 58-4 (1.6 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added dropwise to the reaction system. After the addition was completed, it was kept at 0°C and stirred for 3 hours, and then naturally warmed to room temperature and reacted for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added to mix the sample column chromatography, and the eluent was PE:DCM=1:1 (volume ratio), and about 1.23 g of compound 58-5 was obtained, with a yield of 74.3%. MS: 827.93.

[0290] Synthesis of compound (58):

[0291] Accurately weigh compound 58-5 (0.8 g, 1 mmol), compound 2-8 (0.9 g, 4 mmol) and 1 mL of pyridine, add them into a 50 mL three-necked flask in sequence, add 20 mL of anhydrous chloroform, and follow the subsequent synthesis steps as described for compound (2) to obtain about 576 mg of compound (58), with a yield of 46.0%. MALDI-TOF-MS: 1251.53.

[0292] Synthesis Example 13: Synthesis of Compound (65)

[0293]

[0294] Synthesis of compound 65-1:

[0295] Accurately weigh compound 25-2 (7.7g, 20mmol), compound 58-1 (14.9g, 40mmol), Pd(PPh3)4 (462mg, 0.4mmol), add them into a 500mL three-necked flask, add 250mL anhydrous toluene, and replace nitrogen three times. The entire reaction system is heated to reflux and reacted for 4h. The subsequent synthesis steps refer to the synthesis of compound 25-3 to obtain about 6.72g of compound 65-1, with a yield of 85.9%. MS: 391.23.

[0296] Synthesis of compound 65-2:

[0297] Accurately weigh compound 65-1 (4.7 g, 12 mmol), triphenylphosphine (31.4 g, 120 mmol) and 1,2-dichlorobenzene (o-DCB, 250 mL) into a 500 mL three-necked flask. Heat to 180 °C and stir overnight under nitrogen protection. Remove the solvent to obtain crude compound 65-2 without further purification.

[0298] Synthesis of compound 65-3:

[0299] The crude compound 65-2, potassium carbonate (16.6 g, 120 mmol), potassium iodide (10 g, 60 mmol), and DMF 150 mL were added to a 250 mL three-necked flask. Under nitrogen protection, the mixture was heated to 85 °C for 0.5 h, and then bromoisooctane (23.2 g, 120 mmol) was added and stirred overnight. After cooling to room temperature, water was added and extracted with DCM. The organic phase was dried by adding anhydrous magnesium sulfate, filtered, concentrated, and the solid was added to silica gel for column chromatography. The eluent was PE:DCM=3:1 (volume ratio). About 3.16 g of compound 65-3 was obtained, with a yield of 47.7%. MS: 551.49.

[0300] Synthesis of compound 65-4:

[0301] Accurately weigh compound 65-3 (1.1 g, 2 mmol) and add it to a 25 mL three-necked flask, and add 15 mL DMF. After replacing nitrogen three times, the ice-salt bath was cooled to 0°C, phosphorus oxychloride (0.6 g, 4 mmol) was weighed and slowly added dropwise to the reaction system. After the addition was completed, it was kept at 0°C and stirred for 3 hours, and then naturally warmed to room temperature and reacted for 6 hours. The reaction solution was poured into water to quench, extracted three times with dichloromethane, and the organic phases were combined and dried with anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. Silica gel was added to mix the sample column chromatography, and the eluent was PE:EA=5:1 (volume ratio), and about 0.89 g of compound 65-4 was obtained, with a yield of 73.2%. MS: 607.54.

[0302] Synthesis of compound (65):

[0303] Compound 65-4 (0.6 g, 1 mmol), compound 27-6 (1.1 g, 4 mmol) and 1 mL of pyridine were accurately weighed and added to a 50 mL three-necked flask in sequence. 20 mL of anhydrous chloroform was added. The subsequent synthesis steps were referred to the synthesis of compound (2) to obtain about 631 mg of compound (65) with a yield of 57.5%. MALDI-TOF-MS: 1097.83.

[0304] Organic Photovoltaic Cell (OPV) Device Preparation and Characterization

[0305] This example illustrates the preparation, implementation and characterization of the OPV device provided by the present invention, but the present invention is not limited to the following examples.

[0306] like Figure 1 As shown, the OPV device structure is as follows: indium tin oxide ITO / PEDOT:PSS / active layer / PDINN / Ag.

[0307] Device Example 1:

[0308] 1) ITO substrate cleaning:

[0309] The ITO conductive glass was cleaned with detergent, rinsed, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, then blown dry with nitrogen and treated in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0310] 2) Preparation of anode buffer layer

[0311] PEDOT:PSS (Clevios™ P VP Al 4083) was evenly spin-coated on ITO in air at a spin speed of 4000 rpm for 30 seconds, and dried at 150°C for 15 minutes to obtain an anode buffer layer.

[0312] 3) Preparation of active layer

[0313] In a glove box (inert gas atmosphere), the active layer material solution was evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain a photoactive layer with a total thickness of about 100 nm.

[0314] The active layer material solution preparation method comprises: dissolving the donor material and the acceptor material in toluene to a total concentration of 12.1 mg / mL; and adding 2% by volume of 1-chloronaphthalene as an additive to the solution. The donor material in the active layer material is selected from the polymer PBQx-TCl, the acceptor material is selected from the compound (2), and the mass ratio of the donor material polymer PBQx-TCl ​​to the acceptor material compound (2) is 1:1.2.

[0315]

[0316] 4) Preparation of cathode buffer layer

[0317] After annealing at 80° on a hot plate for 5 minutes, the cathode buffer layer material PDINN (PDINN was dissolved in methanol to prepare a solution with a concentration of 1 mg / mL) was evenly spin-coated on the active layer at a spin-coating speed of 3000 rpm and a spin time of 30 s to obtain a cathode buffer layer.

[0318] 5) Cathode layer preparation

[0319] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at a pressure of 100 mbar to form a cathode layer with a thickness of about 100 nm.

[0320] 6) Packaging

[0321] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0322] Device Example 2:

[0323] The preparation method of device example 2 is the same as that of device example 1, except that the choice of acceptor material in the active layer is different. Specifically, compound (2) in device example 1 is replaced by compound (4).

[0324] Device Example 3:

[0325] The preparation method of device example 3 is the same as that of device example 1, except that the choice of acceptor material in the active layer is different. Specifically, compound (2) in device example 1 is replaced by compound (25).

[0326] Device Example 4:

[0327] The preparation method of device example 4 is the same as that of device example 1, except that the choice of acceptor material in the active layer is different. Specifically, compound (2) in device example 1 is replaced by compound (27).

[0328] Device Example 5:

[0329] The preparation method of device example 5 is the same as that of device example 1, except that the choice of acceptor material in the active layer is different. Specifically, compound (2) in device example 1 is replaced by compound (43).

[0330] The prepared organic photovoltaic cell device was subjected to a performance test. Under the irradiation of standard light from a solar simulator (AM 1.5G), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated, as shown in Table 1.

[0331] Table 1

[0332]

[0333] Device Example 6:

[0334] The preparation method of device example 6 is the same as that of device example 1, except that the choice of acceptor material in the active layer is different. Specifically, compound (2) in device example 1 is replaced by compound (12).

[0335] Device Example 7:

[0336] The preparation method of device example 7 is the same as that of device example 1, except that the choice of acceptor material in the active layer is different. Specifically, compound (2) in device example 1 is replaced by compound (54).

[0337] The prepared organic photovoltaic cell device was tested for performance under indoor light, the cell current-voltage curve was tested under a 3000K LED light source (1000 lux) simulator, and the photoelectric conversion efficiency was calculated, as shown in Table 2.

[0338] Table 2

[0339]

[0340] Device Example 8:

[0341] The preparation method of device embodiment 8 is the same as that of device embodiment 1, except that the preparation method of the active layer material solution is different, as follows:

[0342] The active layer material solution preparation method comprises: dissolving the donor material and the acceptor material in toluene to a total concentration of 12.1 mg / mL; and adding 2% by volume of 1-chloronaphthalene as an additive to the solution. The donor material in the active layer material is selected from the polymer PBQx-TCl, the acceptor material is selected from the compound eC9-2Cl and the compound (10), and the mass ratio of PBQx-TCl:eC9-2Cl:compound (10) is 1:1.1:0.1.

[0343]

[0344] Device Example 9:

[0345] The preparation method of device example 9 is the same as that of device example 8, except that the choice of acceptor material in the active layer is different. Specifically, the acceptor material compound (10) in device example 8 is replaced by compound (14).

[0346] Device Example 10:

[0347] The preparation method of device example 10 is the same as that of device example 8, except that the choice of acceptor material in the active layer is different. Specifically, the acceptor material compound (10) in device example 8 is replaced by compound (29).

[0348] Device Example 11:

[0349] The preparation method of device example 11 is the same as that of device example 8, except that the choice of acceptor material in the active layer is different. Specifically, the acceptor material compound (10) in device example 8 is replaced by compound (32).

[0350] Device Example 12:

[0351] The preparation method of device example 12 is the same as that of device example 8, except that the choice of acceptor material in the active layer is different. Specifically, the acceptor material compound (10) in device example 8 is replaced by compound (58).

[0352] Device Example 13:

[0353] The preparation method of device example 13 is the same as that of device example 8, except that the choice of acceptor material in the active layer is different. Specifically, the acceptor material compound (10) in device example 8 is replaced by compound (65).

[0354] Device Comparison Example 1:

[0355] The preparation method of device comparative example 1 is the same as that of device example 8, except that the preparation method of the active layer material is different, as follows:

[0356] The active layer material preparation method is as follows: dissolving the donor material and the acceptor material in toluene to a total concentration of 12.1 mg / mL; and adding 2% by volume of 1-chloronaphthalene as an additive to the solution. The donor material in the active layer material is selected from the polymer PBQx-TCl, the acceptor material is selected from the compound eC9-2Cl, and the mass ratio of PBQx-TCl:eC9-2Cl is 1:1.2.

[0357] The prepared organic photovoltaic cell device was subjected to a performance test. Under the irradiation of standard light from a solar simulator (AM 1.5G), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated, as shown in Table 3.

[0358] Table 3

[0359]

[0360] It can be seen from the data in Tables 1 to 3 that the organic compound according to the present invention exhibits good exciton dissociation and charge transfer performance when used as an acceptor material in an organic photovoltaic cell, thereby achieving good photoelectric conversion performance.

[0361] 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. An organic compound, characterized in that: The organic compound has a structure as shown in the general formula (I): （I） in: Each occurrence of X is independently selected from CR3R4, NR5, O or S; Each occurrence of Y is independently selected from CR6R7, NR8, O or S; Each occurrence of R3, R4, R5, R6, R7, and R8 is independently selected from -H, -D, -F, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups; R1 and R2 are each independently selected from substituted or unsubstituted straight-chain alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkoxy groups having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkylthio groups having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkylthio groups having 3 to 30 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, and substituted or unsubstituted heteroaromatic groups having 5 to 20 ring atoms; Each occurrence of M is independently selected from O or C(CN)2; Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic groups having 5 to 20 ring atoms; Ar3 and Ar4 are independently selected from substituted or unsubstituted heteroaromatic groups having 5 to 20 ring atoms; The “substituted or unsubstituted” means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a cyclic alkylthio group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups.

2. The organic compound according to claim 1, characterized in that: Ar3 and Ar4 are independently selected from any of the following groups: ； Wherein: Z, at each occurrence, is independently selected from O, S or Se; R9, at each occurrence, is independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkyl having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkoxy having 3 to 30 carbon atoms, substituted or unsubstituted straight-chain alkylthio having 1 to 30 carbon atoms, substituted or unsubstituted branched-chain alkylthio having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; # indicates a fusion site; * indicates a linking site.

3. The organic compound according to claim 2, characterized in that: The organic compound has a structure as shown in the general formula (II-1) or (II-2): 。 4. The organic compound according to claim 2, characterized in that: The organic compound is selected from any one of the general structures of formula (III-1) to (III-8): ； 。 5. The organic compound according to claim 4, characterized in that: Each occurrence of R3 and R4 is independently selected from -H, -D, -F or methyl; each occurrence of R5 is independently selected from -H, -F or methyl; Each occurrence of R6 and R7 is independently selected from -H, -D, -F or methyl; each occurrence of R8 is independently selected from -H, -F or methyl.

6. The organic compound according to claim 1, characterized in that: Said Selected from , Selected from , where * indicates the attachment site; Ar1 and Ar2 are independently selected from * A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R * A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; said R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight-chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

7. The organic compound according to claim 6, characterized in that: The Ar1 and Ar2 are independently selected from any of the following groups: ； in, Each occurrence of V is independently selected from N or CR 10 ; Each occurrence of W is independently selected from O, S, and Se; R 10 Each occurrence is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, branched or cyclic alkoxy having 3 to 10 carbon atoms, straight-chain alkylthio having 1 to 10 carbon atoms, branched or cyclic alkylthio having 3 to 10 carbon atoms, or a group formed by a combination of the above groups.

8. The organic compound according to claim 2, characterized in that: Said R1 and R2 are independently selected from , where R 11 Each occurrence is independently selected from a straight chain alkyl group having 1 to 20 carbon atoms, or a branched chain alkyl group having 3 to 20 carbon atoms; R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a cyclic alkyl group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, or a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups; r is selected from an integer greater than or equal to 0; And / or, each occurrence of R9 is independently selected from -H, -D, or the following groups: 、 ； Among them, R 12 Each occurrence is independently selected from a straight chain alkyl having 1-20 carbon atoms, a branched chain alkyl having 3-20 carbon atoms, a straight chain alkoxy having 1-20 carbon atoms, a branched chain alkoxy having 3-20 carbon atoms, a straight chain alkylthio having 1-20 carbon atoms, or a branched chain alkylthio having 3-20 carbon atoms; Ar5, at each occurrence, is independently selected from an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 5 to 20 ring atoms; R a Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, a cyclic alkyl group having 3-10 carbon atoms, an aromatic group having 6-10 carbon atoms, a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups; R b Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched-chain alkyl having 3-20 carbon atoms, cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched-chain alkoxy having 3-20 carbon atoms, cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched-chain alkylthio having 3-20 carbon atoms, cyclic alkylthio having 3-20 carbon atoms, or a group formed by a combination of the above groups; m1 is selected from integers greater than or equal to 0; n is selected from integers greater than or equal to 0.

9. The organic compound according to claim 1, characterized in that: The organic compound is selected from any of the following structures: 。 10. An organic electronic device, comprising a first electrode, a second electrode, and at least one functional layer located between the first electrode and the second electrode, characterized in that: The at least one functional layer comprises the organic compound according to any one of claims 1 to 9.

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