Alkoxy-substituted organic compound and application thereof

Abstract

The invention relates to the field of organic solar cell materials, in particular to an alkoxy substituted organic compound. The organic compound has an A-DA 'D-A structure and can be used as a photoactive layer acceptor material to be matched with a proper donor material to be applied to an organic solar cell, so that relatively high device performance is realized.

Description

Technical Field

[0001] The invention relates to the field of organic solar cell materials, in particular to an organic compound containing alkoxy substitution and application thereof. Background Art

[0002] With the rapid development of the Internet of Things, various distributed low-power and long-standby microelectronic products (e.g., sensors, watches, calculators, remote controls, hearing aids, and monitors) have put forward new requirements for off-grid energy. Organic photovoltaic cells have become an ideal choice for collecting indoor light photons and performing photoelectric conversion due to their easy-to-adjust absorption spectrum and insignificant charge recombination under low carrier density conditions.

[0003] The molecular design of indoor organic photovoltaic devices is very different from that of outdoor organic photovoltaics. This is because the emission spectrum range of indoor light sources is very different from the standard sunlight AM 1.5G spectrum. The typical color temperature of indoor lighting is 3000-6500K, and its irradiation spectrum is in the visible range of 400-700nm, while the standard sunlight AM 1.5G spectrum range is 300-1100nm. Due to the spectral mismatch, high-efficiency solar cell material systems with near-infrared absorption characteristics are not suitable for indoor applications.

[0004] In order to realize efficient indoor photovoltaic devices, it is necessary to design indoor photovoltaic acceptor materials with suitable absorption spectra that match indoor light sources. In 2021, Hou Jianhui's research group at the Institute of Chemistry, Chinese Academy of Sciences, developed three A-π-D-π-A structured non-condensed ring wide-bandgap non-fullerene acceptors GS-OEH, GS-OC6 and GS-ISO. Among them, the acceptor material GS-ISO was paired with the donor material PM6 under a 500lux LED light source to obtain a photoelectric conversion efficiency of 28.37% (Adv. Mater. 2022, 34(5), 2108090). In 2022, Hou Jianhui's research group obtained a photoelectric conversion efficiency of 31.09% by pairing the acceptor material FTCC-Br with the donor material PB4 under a 1000lux LED light source (J. Mater. Chem. A, 2023, 11, 983-991).

[0005] Although the photoelectric conversion efficiency of indoor organic solar cell devices has exceeded 30%, there are currently only a few acceptor materials suitable for indoor photovoltaic devices. The limited development of acceptor materials suitable for indoor use has hindered the development of indoor organic photovoltaics. Summary of the invention

[0006] The purpose of the present invention is to develop a new type of active layer receptor material suitable for indoor organic photovoltaics, so as to promote the development and industrialization of indoor organic photovoltaic technology.

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

[0008] An alkoxy-substituted organic compound having a structure as shown in general formula (I):

[0009]

[0010] Wherein: Z, at each occurrence, is independently selected from O, S or Se;

[0011] Each occurrence of R1 is independently selected from a straight-chain alkyl group having 1-30 C atoms, a branched or cyclic alkyl group having 3-30 C atoms, an aromatic group having 6-20 carbon atoms, a heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups;

[0012] Each occurrence of R2 is independently selected from a linear alkoxy group having 1 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a * Substituted aromatic groups having 6 to 20 carbon atoms, or one or more R * Substituted heteroaromatic groups having 5 to 20 ring atoms;

[0013] R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 20 carbon atoms, branched-chain alkyl having 3 to 20 carbon atoms, straight-chain alkoxy having 1 to 20 carbon atoms, branched-chain alkoxy having 3 to 20 carbon atoms, straight-chain alkylthio having 1 to 20 carbon atoms, branched-chain alkylthio having 3 to 20 carbon atoms, or a group formed by a combination of the above groups; and at least one R * is selected from a linear alkoxy group having 1 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms;

[0014] Each occurrence of M is independently selected from O or C(CN)2;

[0015] Each occurrence of R3 and R4 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a group formed by a combination of the above groups;

[0016] Ar1 is selected from unsubstituted or substituted with one or more R # Substituted heteroaromatic groups having 5 to 30 ring atoms;

[0017] R #Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups.

[0018] In a preferred embodiment, the alkoxy-substituted organic compound has a structure as shown in the general formula (II-1) or the general formula (II-2):

[0019]

[0020] In one embodiment, each occurrence of R2 is independently selected from a linear alkoxy group having 1-20 C atoms or a branched alkoxy group having 3-20 C atoms.

[0021] Furthermore, the alkoxy-substituted organic compound has a structure as shown in the general formula (III-1) or the general formula (III-2):

[0022]

[0023] Wherein: R5 each occurrence is independently selected from a straight chain alkyl group having 1-20 C atoms, or a branched chain alkyl group having 3-20 C atoms.

[0024] Preferably, each occurrence of R5 is independently selected from a straight chain alkyl group having 1 to 16 C atoms, or a branched chain alkyl group having 3 to 16 C atoms.

[0025] Specifically, each occurrence of R5 is independently selected from -C 10 H 21 , -C 11 H 23 , -C 12 H 25 , * represents the ligation site.

[0026] In another embodiment, each occurrence of R2 is independently selected from one or more R * Substituted aromatic groups having 6 to 10 carbon atoms, or one or more R * Substituted heteroaromatic group having 5-10 ring atoms; R * Each occurrence is independently selected from straight-chain alkoxy having 1-20 C atoms, or branched or cyclic alkoxy having 3-20 C atoms.

[0027] Furthermore, the alkoxy-substituted organic compound has a structure as shown in the general formula (III-3) or the general formula (III-4):

[0028]

[0029] Wherein: Ar2, at each occurrence, is independently selected from an aromatic group having 6 to 10 carbon atoms, or a heteroaromatic group having 5 to 10 ring atoms;

[0030] Each occurrence of R6 is independently selected from a straight chain alkyl group having 1-20 C atoms, or a branched chain alkyl group having 3-20 C atoms.

[0031] In a preferred embodiment, each occurrence of Ar2 is independently selected from phenyl, naphthyl, thienyl, furanyl, stanphenyl, or thienothiphenyl, but is not limited thereto.

[0032] In one embodiment, each occurrence of R6 is independently selected from a straight chain alkyl group having 1-16 C atoms, or a branched chain alkyl group having 3-16 C atoms. Further, each occurrence of R6 is independently selected from

[0033] Specifically, the Each occurrence is independently selected from the following groups:

[0034]

[0035] In one embodiment, each occurrence of R1 is independently selected from a straight chain alkyl group having 1-20 C atoms, a branched chain alkyl group having 3-20 C atoms.

[0036] Furthermore, each occurrence of R1 is independently selected from a straight chain alkyl group having 6-20 C atoms, a branched chain alkyl group having 6-20 C atoms.

[0037] Furthermore, each occurrence of R1 is independently selected from a straight chain alkyl group having 6 to 16 C atoms, a branched chain alkyl group having 6 to 16 C atoms. Specifically, each occurrence of R1 is independently selected from

[0038]

[0039] In one embodiment, the Ar1 is selected from the following groups:

[0040]

[0041] in:

[0042] W is selected from O, S, Se or NR7;

[0043] Each occurrence of X is independently selected from CR8 or N;

[0044] R7, at each occurrence, is independently selected from a straight chain alkyl group having 1 to 20 C atoms, or a branched chain alkyl group having 3 to 20 C atoms;

[0045] Each occurrence of R8 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched or 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;

[0046] # indicates a fusion site, which is selected from a C atom.

[0047] In one embodiment, the group (A-1) is preferably selected from

[0048] In one embodiment, the group (A-2) is preferably selected from Preferably, each occurrence of R8 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, phenyl, thienyl, substituted by one or more R a Substituted phenyl, one or more R a Substituted thienyl; R a Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms.

[0049] In a specific embodiment, the group (A-2) is preferably selected from the following groups:

[0050]

[0051] In one embodiment, the group (A-3) is preferably selected from

[0052] In one embodiment, the group (A-4) is preferably selected from Preferably, each occurrence of R8 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano or nitro.

[0053] In a specific embodiment, the group (A-4) is preferably selected from the following groups:

[0054]

[0055] In one embodiment, the group (A-5) is preferably selected from Preferably, each occurrence of R8 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, phenyl, thienyl, substituted by one or more R a Substituted phenyl, one or more R a Substituted thienyl; R a Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms.

[0056] In a specific embodiment, the group (A-5) is preferably selected from the following groups:

[0057]

[0058] In one embodiment, the group (A-6) is preferably selected from Preferably, each occurrence of R8 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms, phenyl, thienyl, substituted by one or more R a Substituted phenyl, one or more R a Substituted thienyl; R a Each occurrence is independently selected from -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1 to 10 carbon atoms, branched or cyclic alkyl having 3 to 10 carbon atoms.

[0059] In a specific embodiment, the group (A-6) is preferably selected from the following groups:

[0060]

[0061] In one embodiment, the group (A-7) is preferably selected from Preferably, each occurrence of R8 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, straight chain alkyl having 1-10 carbon atoms, branched or cyclic alkyl having 3-10 carbon atoms.

[0062] In a specific embodiment, the group (A-7) is preferably selected from the following groups:

[0063]

[0064] In one embodiment, each occurrence of R3 and R4 is independently selected from -H, -D, -F, -CF3, -Cl, -Br, -I, cyano, nitro, a straight chain alkyl group having 1-6 carbon atoms, or a branched chain alkyl group having 3-6 carbon atoms.

[0065] In a specific embodiment, the Each occurrence is independently selected from the following groups:

[0066]

[0067] Wherein: * indicates the connection site.

[0068] In a specific embodiment, the Each occurrence is independently selected from the following groups:

[0069]

[0070] The alkoxy-substituted organic compound according to the present invention is selected from the following structures, but is not limited thereto:

[0071]

[0072]

[0073]

[0074]

[0075] Furthermore, the present invention also relates to an acceptor material for indoor photovoltaics, wherein the acceptor material for indoor photovoltaics is selected from the above-mentioned organic compounds containing alkoxy substitution.

[0076] Furthermore, the present invention also relates to a mixture, the mixture comprising the above-mentioned alkoxy-substituted organic compound and at least another organic functional material. Preferably, the another organic functional material is selected from a photoactive layer donor material or a photoactive layer acceptor material.

[0077] In one embodiment, the photoactive layer donor material is selected from polymer donor materials. Preferably, the polymer donor material can be selected from polythiophene material systems, such as P3AT, P3HT, P3OT, P3DDT, etc.; fluorene-containing polymer material systems, such as PF8BT, etc.; novel structure narrow band gap polymer material systems, such as benzothiadiazoles (BT, DBT), quinoxalines (QU, PQ), pyrazines (TP, PQ) and electron-rich groups (such as thiophene derivatives) copolymerized, such as PCDTBT, PCPDTBT, PFO-DBT, PTB7, PM6, J52, etc.

[0078] In a specific embodiment, the photoactive layer donor material is 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, and J52-Cl, but is not limited thereto:

[0079]

[0080] Wherein: n represents the number of repeating units, which is selected from an integer greater than 1.

[0081] In one embodiment, the photoactive layer acceptor material is selected from non-fullerene acceptor materials or fullerene derivative acceptor materials. Preferably, the photoactive layer acceptor material is selected from Y6, L8-BO, BTP-H2, N3, BTP-eC9, PY-IT, PTBPT, PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerene, etc., but not limited thereto.

[0082] Furthermore, the present invention also relates to a composition, which comprises the above-mentioned alkoxy-substituted organic compound or mixture, and at least one organic solvent.

[0083] Preferably, the organic solvent can be selected from one 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, and mesitylene, or a mixture of two or more thereof.

[0084] Preferably, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform, but is not limited thereto.

[0085] In one embodiment, the total concentration of the mixture in the organic solvent is 7-30 mg / mL; further, the total concentration of the mixture in the organic solvent is 10-20 mg / mL.

[0086] It should be noted that the above-mentioned organic solvent may be evaporated from the solvent system to form a thin film including the above-mentioned organic compound.

[0087] 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.

[0088] It should be noted that the present application also relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device. In one embodiment, the above composition is used to prepare an organic electronic device by a printing or coating preparation method. The printing or coating preparation method can be, but is not limited to, inkjet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slit extrusion coating, etc. The preferred ones are slit coating, spin coating and inkjet printing.

[0089] Furthermore, the present invention also relates to an organic solar cell, which comprises at least an anode, a cathode and a photoactive layer located between the anode and the cathode, wherein the photoactive layer comprises the alkoxy-substituted organic compound or mixture as described above, or is prepared from the above composition.

[0090] The materials used to prepare the cathode and anode can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides, such as ZnO:Al or SnO2:Sb, etc.; and conductive polymers, such as PEDOT:PSS, polypyrrole and polyaniline, etc.; or materials with a multilayer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2 and Al:BaF2:Ba, etc., but are not limited thereto.

[0091] In a specific embodiment, the photoactive layer comprises a photoactive layer donor material and a photoactive layer acceptor material. The photoactive layer donor material is described as above, and 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, and J52-Cl, but is not limited thereto.

[0092] The photoactive layer acceptor material at least comprises the alkoxy-substituted 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 fullerene acceptor materials or fullerene derivative acceptor materials. Preferably, the another photoactive layer acceptor material is selected from Y6, L8-BO, BTP-H2, N3, BTP-eC9, PY-IT, PTBPT, PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), indene-containing fullerene, etc., but is not limited thereto.

[0093] In one embodiment, the mass ratio of the photoactive layer donor material to the photoactive layer acceptor material in the photoactive layer is selected from 0.8:1.5-1.5:0.8; further, selected from 1:1-1:1.5; further, selected from 1:1-1:1.3.

[0094] Further, the photoactive layer may be formed by dissolving the photoactive material in an organic solvent and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spray coating, doctor blade, slit coating, and inkjet printing, but is not limited thereto.

[0095] In one embodiment, the organic solar cell further comprises a cathode buffer layer, wherein the cathode buffer layer is located between the cathode and the photoactive layer.

[0096] 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.

[0097] In one embodiment, the organic solar cell further comprises an anode buffer layer, wherein the anode buffer layer is located between the anode and the photoactive layer.

[0098] Preferably, 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.

[0099] It should be noted that, in order to improve the performance of the organic solar cell device, the organic solar cell may further include other functional layers, including but not limited to a charge blocking layer and a charge transport layer.

[0100] 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.

[0101] In one embodiment, as a substrate, a substrate having excellent transparency, surface smoothness, ease of operation 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 or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyparaxylene (Parylene), etc., but is not limited thereto, and a substrate commonly used for organic solar cells may also be used.

[0102] In a specific embodiment, the organic solar cell is stacked with an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer and a cathode in sequence from bottom to top, and the photoactive layer comprises the alkoxy-substituted organic compound or mixture as described above, or is prepared from the above composition.

[0103] The organic solar cell according to the present invention is mainly used for indoor photovoltaics, preferably for weak-light and low-power devices, including but not limited to: electronic price tags, Internet of Things sensors, smart homes, etc.

[0104] Compared with the prior art, the present invention has the following significant advantages:

[0105] The alkoxy-substituted organic compound provided by the present invention has an A-DA'DA structure, and an alkoxy group is introduced into the shoulder of the large condensed ring core (DA'D) and an electron-withdrawing end group A is introduced into the The electron-donating capacity of the central core and the end group can be weakened, causing the absorption spectrum of the organic compound to blue-shift, making it more compatible with indoor light sources.

[0106] At the same time, the alkoxy-substituted organic compound disclosed in the present invention as a photoactive layer acceptor material is matched with a suitable donor material and exhibits good molecular morphology and stability, thereby achieving a higher indoor photoelectric conversion efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0107] Figure 1 It is a schematic diagram of the structure of an embodiment of an organic solar cell (OPV) device of the present invention. DETAILED DESCRIPTION

[0108] 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.

[0109] 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").

[0110] In the present invention, organic photovoltaic device, organic solar cell, OPV and OSC have the same meaning and can be interchangeable.

[0111] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0112] 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 as or different from each other.

[0113] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] In the present invention, the number of carbon atoms in the straight chain 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 in the branched chain 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 straight chain alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, -C 10H 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0128] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0129] Synthesis Example of Alkoxy-Substituted Organic Compounds

[0130] Example 1: Synthesis of organic compound (H-1)

[0131]

[0132] Synthesis of organic compound (H-1):

[0133] Accurately weigh compound H-1-1 (600 mg, 0.5 mmol) and H-1-2 (440 mg, 2.2 mmol) into a 250 mL three-necked flask, add 100 mL of chloroform, stir to dissolve, replace nitrogen three times, add 2 mL of pyridine, heat to 85 ° C, react for 12 h, and remove most of the solvent by vacuum distillation. Then, drop the remaining reaction solution into methanol for precipitation, and use a mixed solvent of PE:DCM = 1:1 (volume ratio) as an eluent for column chromatography. After concentrating the organic phase, precipitate it in methanol, filter it, and dry it to obtain about 550 mg of an organic compound (H-1) with a yield of 70.3%. MALDI-TOF-MS: 1563.47.

[0134] Example 2: Synthesis of organic compound (H-2)

[0135]

[0136] Synthesis of organic compound (H-2):

[0137] Accurately weigh compound H-1-1 (600 mg, 0.5 mmol) and H-2-1 (516 mg, 2.2 mmol) into a 250 mL three-necked flask, add 100 mL of chloroform, stir to dissolve, replace nitrogen three times, add 2 mL of pyridine, heat to 85 ° C, react for 12 h, and remove most of the solvent by vacuum distillation. Then, drop the remaining reaction solution into methanol for precipitation, and use a mixed solvent of PE:DCM = 3:1 (volume ratio) as an eluent for column chromatography. After concentrating the organic phase, precipitate it in methanol, filter it, and dry it to obtain an organic compound (H-2) of about 558 mg, with a yield of 68.4%, MALDI-TOF-MS: 1632.79.

[0138] Example 3: Synthesis of organic compound (H-3)

[0139]

[0140] Synthesis of organic compound (H-3):

[0141] Accurately weigh compound H-1-1 (600 mg, 0.5 mmol) and H-3-1 (614 mg, 2.2 mmol) into a 250 mL three-necked flask, add 100 mL of chloroform, stir to dissolve, replace nitrogen three times, add 2 mL of pyridine, heat to 85 ° C, react for 12 h, and remove most of the solvent by vacuum distillation. Then, drop the remaining reaction solution into methanol for precipitation, and use a mixed solvent of PE:DCM = 2:1 (volume ratio) as an eluent for column chromatography. After concentrating the organic phase, precipitate it in methanol, filter it, and dry it to obtain an organic compound (H-3) of about 630 mg, with a yield of 73.2%, MALDI-TOF-MS: 1722.41.

[0142] Example 4: Synthesis of organic compound (H-36)

[0143]

[0144] Synthesis of organic compound (H-36):

[0145] Accurately weigh compound H-1-1 (600 mg, 0.5 mmol) and H-36-1 (614 mg, 2.2 mmol) into a 250 mL three-necked flask, add 100 mL of chloroform, stir to dissolve, replace nitrogen three times, add 2 mL of pyridine, heat to 85 ° C, react for 12 h, and remove most of the solvent by vacuum distillation. Then, drop the remaining reaction solution into methanol for precipitation, and use a mixed solvent of PE:DCM = 4:1 (volume ratio) as an eluent for column chromatography. After concentrating the organic phase, precipitate it in methanol, filter it, and dry it to obtain an organic compound (H-36) of about 566 mg, with a yield of 65.7%, MALDI-TOF-MS: 1722.67.

[0146] Example 5: Synthesis of organic compound (H-11)

[0147]

[0148] Synthesis of organic compound (H-11):

[0149] Accurately weigh compound H-11-1 (628 mg, 0.5 mmol) and H-2-1 (516 mg, 2.2 mmol) into a 250 mL three-necked flask, add 100 mL of chloroform, stir to dissolve, replace nitrogen three times, add 2 mL of pyridine, heat to 85 ° C, react for 12 h, and remove most of the solvent by vacuum distillation. Then, drop the remaining reaction solution into methanol for precipitation, and use a mixed solvent of PE:DCM = 4:1 (volume ratio) as an eluent for column chromatography. After concentrating the organic phase, precipitate in methanol, filter, and dry to obtain an organic compound (H-11) of about 605 mg, with a yield of 71.6%, MALDI-TOF-MS: 1689.42.

[0150] Example 6: Synthesis of organic compound (H-40)

[0151]

[0152] Synthesis of organic compound (H-40):

[0153] Accurately weigh compound H-11-1 (628 mg, 0.5 mmol) and H-40-1 (516 mg, 2.2 mmol) into a 250 mL three-necked flask, add 100 mL of chloroform, stir to dissolve, replace nitrogen three times, add 2 mL of pyridine, heat to 85 ° C, react for 12 h, and remove most of the solvent by vacuum distillation. Then, drop the remaining reaction solution into methanol for precipitation, and use a mixed solvent of PE:DCM = 4:1 (volume ratio) as an eluent for column chromatography. After concentrating the organic phase, precipitate it in methanol, filter it, and dry it to obtain an organic compound (H-40) of about 613 mg, with a yield of 72.6%, MALDI-TOF-MS: 1689.01.

[0154] Example 7: Synthesis of organic compound (H-21)

[0155]

[0156] Synthesis of compound H-21-3:

[0157] Accurately weigh compound H-21-1 (712 mg, 2 mmol) and H-21-2 (2.34 g, 4 mmol) into a 250 mL three-necked flask, add 100 mL of toluene, stir to dissolve, replace nitrogen three times, then add bis(triphenylphosphine)palladium dichloride (42 mg, 0.06 mmol), raise the temperature to 100 ° C and react for 1 hour. After the reaction solution is cooled to room temperature, it is poured into water to quench, extracted with ethyl acetate, concentrated, and purified by column chromatography (PE: EA = 50: 1 (volume ratio) as eluent) to obtain about 1.49 g of compound H-21-3, with a yield of 94.7%. MS: 787.11

[0158] Synthesis of compound H-21-4:

[0159] Accurately weigh triphenylphosphine (1.68g, 6.4mmol) and add it to a 100mL three-necked flask. Heat to 100℃ to dissolve it, then add 10mL of o-dichlorobenzene, then add compound H-21-3 (1.26g, 1.6mmol), heat to 160℃, and react for 4h. After the reaction solution is cooled to room temperature, pour it into water and stir, extract with dichloromethane, and purify it by column chromatography (PE:EA=6:1 (volume ratio) as eluent) to obtain about 753mg of compound H-21-4, with a yield of 65.1%. MS: 722.86

[0160] Synthesis of compound H-21-6:

[0161] Accurately weigh compound H-21-4 (578 mg, 0.8 mmol) and add it to a 100 mL three-necked flask. Dissolve it with 20 ml N, N-dimethylacetamide and add potassium carbonate (442 mg, 3.2 mmol). Replace nitrogen 3 times. Stir for 10 minutes and then drop compound H-21-5 (977 mg, 3.2 mmol). Then raise the temperature to 85 °C and react for 12 hours. Pour the reaction solution into water, extract with ethyl acetate, and purify by column chromatography (petroleum ether as eluent) to obtain about 867 mg of compound H-21-6, with a yield of 92.5%. MALDI-TOF-MS: 1171.59

[0162] Synthesis of compound H-21-7:

[0163] Accurately weigh compound H-21-6 (703 mg, 0.6 mmol) and 1,2,5-thiadiazole-3,4-diamine (139 mg, 1.2 mmol), add to a 100 mL three-necked flask, then add 30 mL toluene and 6 mL acetic acid, replace nitrogen 3 times, and heat to reflux for 24 hours. Then cool the reaction solution to room temperature, add water and chloroform for separation and extraction, dry the organic phase with anhydrous sodium sulfate, concentrate, and purify by column chromatography (PE:DCM = 5:1 (volume ratio) as eluent) to obtain about 476 mg of compound H-21-7, with a yield of 63.3%. MALDI-TOF-MS: 1252.35

[0164] Synthesis of compound H-21-8:

[0165] Accurately weigh compound H-21-7 (251 mg, 0.2 mmol), add it to a 100 mL three-necked flask, dissolve it with 20 mL of anhydrous N, N-dimethylformamide, replace nitrogen three times, cool the temperature to below 0°C with an ice-salt bath, then drop 0.66 mL of phosphorus oxychloride, stir for 30 minutes, heat to 90°C and react for 12 hours. Pour the reaction solution into water to quench, extract with ethyl acetate, and purify by column chromatography (PE:EA=20:1 (volume ratio) as eluent) to obtain about 198 mg of compound H-21-8, with a yield of 75.7%. MALDI-TOF-MS: 1308.06

[0166] Synthesis of organic compound (H-21):

[0167] Accurately weigh compound H-21-8 (66 mg, 0.05 mmol) and compound H-3-1 (56 mg, 0.2 mmol) and add them to a 100 mL three-necked flask, add 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.2 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase and precipitated in methanol, filtered, and dried to obtain about 69 mg of organic compound (H-21), with a yield of 76.0%, MALDI-TOF-MS: 1829.65.

[0168] Example 8: Synthesis of organic compound (H-44)

[0169]

[0170] Synthesis of organic compound (H-44):

[0171] Accurately weigh compound H-21-8 (66 mg, 0.05 mmol) and H-36-1 (56 mg, 0.2 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.2 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain about 67 mg of organic compound (H-44), with a yield of 73.1%, MALDI-TOF-MS: 1830.48.

[0172] Example 9: Synthesis of organic compound (H-26)

[0173]

[0174] Synthesis of compound H-26-2:

[0175] Accurately weigh compound H-23-1 (768 mg, 2 mmol) and H-26-2 (2.45 g, 4 mmol) into a 250 mL three-necked flask, add 100 mL of toluene, stir to dissolve, replace nitrogen three times, then add bis(triphenylphosphine)palladium dichloride (42.11 mg, 0.06 mmol), raise the temperature to 100 ° C and react for 1 hour. After the reaction solution is cooled to room temperature, it is poured into water to quench, extracted with ethyl acetate, concentrated, and purified by column chromatography (PE: EA = 50: 1 (volume ratio) as eluent) to obtain about 1.63 g of compound H-26-2, with a yield of 93.5%. MS: 871.68

[0176] Synthesis of compound H-26-3:

[0177] Accurately weigh the compound triphenylphosphine (1.57 g, 6 mmol) and add it to a 100 mL three-necked flask. Heat to 100 ° C to dissolve it, then add 10 mL of o-dichlorobenzene, then add H-26-2 (1.31 g, 1.5 mmol), heat to 160 ° C, and react for 4 hours. After the reaction solution is cooled to room temperature, pour it into water and stir, extract with dichloromethane, and purify it by column chromatography (PE: EA = 6: 1 (volume ratio) as eluent) to obtain about 888 mg of H-26-3, with a yield of 73.3%. MS: 807.31

[0178] Synthesis of compound H-26-5:

[0179] Accurately weigh compound H-26-3 (807 mg, 1 mmol) and add it to a 100 mL three-necked flask. Dissolve it with 20 ml N, N-dimethylacetamide and add potassium carbonate (552 mg, 4 mmol). Replace nitrogen three times. Stir for 10 minutes and then drop compound H-21-4 (997 mg, 4 mmol). Then raise the temperature to 85 °C and react for 12 hours. Pour the reaction solution into water, extract with ethyl acetate, and purify by column chromatography (petroleum ether as eluent) to obtain about 1.02 g of compound H-26-5 with a yield of 89.2%. MALDI-TOF-MS: 1144.52

[0180] Synthesis of compound H-26-6:

[0181] Accurately weigh compound H-26-5 (915 mg, 0.8 mmol) and add it to a 100 mL three-necked flask, add 20 mL tetrahydrofuran and stir to dissolve, replace nitrogen 3 times, cool to 0 ° C, add 8 mL lithium aluminum hydride (2.5 M), and then heat to 80 ° C to react for 18 hours. Then add water and dichloromethane to extract and separate the liquids, wash the organic phase with saturated brine, dry with magnesium sulfate, and concentrate to obtain about 736 mg of compound H-26-6, with a yield of 82.5%. MALDI-TOF-MS: 1115.97

[0182] Synthesis of compound H-26-8:

[0183] Accurately weigh compound H-26-6 (558 mg, 0.5 mmol) and add it to a 100 mL three-necked flask, add 10 mL ethanol and 10 mL acetic acid, stir and dissolve, replace nitrogen 3 times, add compound H-26-7 (208 mg, 1 mmol), heat to 100 ° C and react for 18 hours. Then cool to room temperature, add water and dichloromethane to extract and separate the liquid, wash the organic phase with saturated brine, dry, concentrate and purify by column chromatography to obtain about 514 mg of compound H-26-8, with a yield of 79.8%. MALDI-TOF-MS: 1287.79

[0184] Synthesis of compound H-26-9:

[0185] Accurately weigh compound H-26-8 (386 mg, 0.3 mmol), add it to a 100 mL three-necked flask, dissolve it with 9 ml of anhydrous N, N-dimethylformamide, replace nitrogen three times, cool the temperature to below 0°C with an ice-salt bath, then drop 0.92 ml of phosphorus oxychloride, stir for 30 minutes, heat to 90°C and react for 12 hours. Pour the reaction solution into water to quench, extract with ethyl acetate, and purify by column chromatography (PE:EA=20:1 (volume ratio) as eluent) to obtain about 336 mg of compound H-26-9, with a yield of 83.3%. MALDI-TOF-MS: 1344.19

[0186] Synthesis of organic compound (H-26):

[0187] Accurately weigh compound H-26-9 (135 mg, 0.1 mmol) and H-3-1 (112 mg, 0.4 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.4 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain about 132 mg of organic compound (H-26), with a yield of 70.5%, MALDI-TOF-MS: 1865.77.

[0188] Example 10: Synthesis of Compound (H-27)

[0189]

[0190] Synthesis of compound H-27-1:

[0191] Accurately weigh compound H-1-1 (600 mg, 0.5 mmol) and add it to a 100 mL three-necked flask, add 20 mL of tetrahydrofuran and stir to dissolve, replace nitrogen 3 times, cool to 0°C, add 5 mL of lithium aluminum hydride (2.5 M), and then heat to 80°C to react for 18 hours. Then add water and dichloromethane to extract and separate the liquids, wash the organic phase with saturated brine, dry with magnesium sulfate, and concentrate to obtain about 490 mg of compound H-27-1, with a yield of 83.6%. MALDI-TOF-MS: 1171.92

[0192] Synthesis of compound H-27-3:

[0193] Accurately weigh compound H-27-1 (352 mg, 0.3 mmol) and add it to a 100 mL three-necked flask, add 10 mL ethanol and 10 mL acetic acid, stir and dissolve, replace nitrogen 3 times, then add compound H-27-2 (110 mg, 0.6 mmol), heat to 100 ° C and react for 18 hours. Then cool to room temperature, add water and dichloromethane to extract and separate the liquid, wash the organic phase with saturated brine, dry, concentrate and purify by column chromatography to obtain about 330 mg of compound H-27-3, with a yield of 83.4%. MALDI-TOF-MS: 1317.80

[0194] Synthesis of organic compound (H-27):

[0195] Accurately weigh compound H-27-3 (132 mg, 0.1 mmol) and H-2-1 (94 mg, 0.4 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.4 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain about 122 mg of organic compound (H-27), with a yield of 69.4%, MALDI-TOF-MS: 1750.83.

[0196] Example 11: Synthesis of organic compound (H-23)

[0197]

[0198] Synthesis of compound H-23-3:

[0199] Accurately weigh compound H-23-1 (768 mg, 2 mmol) and H-23-2 (2.45 g, 4 mmol) into a 250 mL three-necked flask, add 100 mL of toluene, stir to dissolve, replace nitrogen three times, then add bis(triphenylphosphine)palladium dichloride (42 mg, 0.06 mmol), raise the temperature to 100 ° C and react for 1 hour. After the reaction solution is cooled to room temperature, it is poured into water to quench, extracted with ethyl acetate, concentrated, and purified by column chromatography (PE: EA = 50: 1 (volume ratio) as eluent) to obtain about 1.67 g of compound H-23-3, with a yield of 95.8%. MS: 871.63

[0200] Synthesis of compound H-23-4:

[0201] Accurately weigh the compound triphenylphosphine (1.57 g, 6 mmol) and add it to a 100 mL three-necked flask. Heat to 100 ° C to dissolve it, then add 10 mL of o-dichlorobenzene, then add H-23-3 (1.31 g, 1.5 mmol), heat to 160 ° C, and react for 4 hours. After the reaction solution is cooled to room temperature, pour it into water and stir, extract with dichloromethane, and purify it by column chromatography (PE: EA = 7: 1 (volume ratio) as eluent) to obtain about 904 mg of compound H-23-4, with a yield of 74.7%. MS: 806.78

[0202] Synthesis of compound H-23-6:

[0203] Accurately weigh compound H-23-4 (807 mg, 1 mmol) and add it to a 100 mL three-necked flask. Dissolve it with 20 ml N, N-dimethylacetamide and add potassium carbonate (552 mg, 4 mmol). Replace nitrogen 3 times. Stir for 10 minutes and then drop compound H-21-5 (1.22 g, 4 mmol). Then raise the temperature to 85 °C and react for 12 hours. Pour the reaction solution into water, extract with ethyl acetate, and purify by column chromatography (petroleum ether as eluent) to obtain about 1.12 g of compound H-23-6, with a yield of 89.2%. MALDI-TOF-MS: 1256.30

[0204] Synthesis of compound H-23-7:

[0205] Accurately weigh compound H-23-6 (1.0 g, 0.8 mmol) and add it to a 100 mL three-necked flask, dissolve it with 50 ml tetrahydrofuran, add lithium aluminum hydride (151.8 mg, 4 mmol) under nitrogen protection, heat to reflux reaction for 12 h, cool to 0 ° C, add 30 mL of water, then extract with dichloromethane, dry with sodium sulfate, and concentrate the solvent. The crude product is added to a 100 mL three-necked flask, 50 mL of chloroform is added to dissolve, 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) (363.2 mg, 1.6 mmol), 1,2-diamino-4,5-dibromobenzene (1.06 g, 4 mmol) are added in sequence, stirred at room temperature for 6 h, the solvent is concentrated, and purified by column chromatography (PE: EA = 15: 1 (volume ratio) as eluent) to obtain about 931 mg of compound H-23-7, with a yield of 79.8%. MALDI-TOF-MS:1457.58

[0206] Synthesis of compound H-23-8:

[0207] Accurately weigh compound H-23-7 (437.37 mg, 0.3 mmol), add it to a 100 mL three-necked flask, dissolve it with 9 ml of anhydrous N, N-dimethylformamide, replace nitrogen three times, cool the temperature to below 0°C with an ice-salt bath, then drop 0.92 ml of phosphorus oxychloride, stir for 30 minutes, heat to 90°C and react for 12 hours. Pour the reaction solution into water to quench, extract with ethyl acetate, and purify by column chromatography (PE:EA=20:1 (volume ratio) as eluent) to obtain about 346 mg of compound H-23-8, with a yield of 76.1%. MALDI-TOF-MS: 1513.49

[0208] Synthesis of organic compound (H-23):

[0209] Accurately weigh compound H-23-8 (152 mg, 0.1 mmol) and H-2-1 (94 mg, 0.4 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.4 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain about 142 mg of organic compound (H-23), with a yield of 72.9%, MALDI-TOF-MS: 1946.85.

[0210] Example 12: Synthesis of organic compound (H-45)

[0211]

[0212] Synthesis of organic compound (H-45):

[0213] Accurately weigh compound H-23-8 (76 mg, 0.05 mmol) and H-36-1 (56 mg, 0.2 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.2 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain an organic compound (H-45) of about 76 mg, with a yield of 74.3%, MALDI-TOF-MS: 2035.91.

[0214] Example 13: Synthesis of organic compound (H-53)

[0215]

[0216] Synthesis of compound H-53-2:

[0217] Accurately weigh compound H-23-1 (768 mg, 2 mmol) and H-53-1 (2.81 g, 4 mmol) into a 250 mL three-necked flask, add 100 mL of toluene, stir to dissolve, replace nitrogen three times, then add bis(triphenylphosphine)palladium dichloride (42 mg, 0.06 mmol), raise the temperature to 100 ° C and react for 1 hour. After the reaction solution is cooled to room temperature, it is poured into water for quenching, extracted with ethyl acetate, concentrated, and purified by column chromatography (PE: EA = 50: 1 (volume ratio) as eluent) to obtain about 1.92 g of compound H-53-2, with a yield of 93.8%. MS: 1023.68

[0218] Synthesis of compound H-53-3:

[0219] Accurately weigh the compound triphenylphosphine (1.57 g, 6 mmol) and add it to a 100 mL three-necked flask. Heat to 100 ° C to dissolve it, then add 10 mL of o-dichlorobenzene, then add H-53-2 (1.38 g, 1.5 mmol), heat to 160 ° C, and react for 4 hours. After the reaction solution is cooled to room temperature, pour it into water and stir, extract with dichloromethane, and purify it by column chromatography (PE: EA = 6: 1 (volume ratio) as eluent) to obtain about 1.09 g of compound H-53-3, with a yield of 75.7%. MS: 958.81

[0220] Synthesis of compound H-53-5:

[0221] Accurately weigh compound H-53-3 (959 mg, 1 mmol) and add it to a 100 mL three-necked flask. Dissolve it with 20 ml N, N-dimethylacetamide and then add potassium carbonate (552 mg, 4 mmol). Replace nitrogen three times. Stir for 10 minutes and then drop compound H-26-4 (997 mg, 4 mmol). Then raise the temperature to 85 °C and react for 12 hours. Pour the reaction solution into water, extract with ethyl acetate, and purify by column chromatography (petroleum ether as eluent) to obtain about 1.20 g of compound H-53-5, with a yield of 92.6%. MALDI-TOF-MS: 1295.75

[0222] Synthesis of compound H-53-6:

[0223] Accurately weigh compound H-53-5 (1.04 g, 0.8 mmol), add it to a 100 mL three-necked flask, dissolve it with 24 ml of anhydrous N, N-dimethylformamide, replace nitrogen three times, cool the temperature to below 0°C with an ice-salt bath, then drop 2.64 mL of phosphorus oxychloride, stir for 30 minutes, heat to 90°C and react for 12 hours. Pour the reaction solution into water to quench, extract with ethyl acetate, and purify by column chromatography (PE:EA=20:1 (volume ratio) as eluent) to obtain about 852 mg of compound H-53-6, with a yield of 78.7%. MALDI-TOF-MS: 1352.17

[0224] Synthesis of organic compound (H-53):

[0225] Accurately weigh compound H-53-6 (135 mg, 0.1 mmol) and H-2-1 (112 mg, 0.4 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.4 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain about 125 mg of organic compound (H-53), with a yield of 70.0%, MALDI-TOF-MS: 1785.71.

[0226] Example 14: Synthesis of organic compound (H-62)

[0227]

[0228] Synthesis of organic compound (H-62):

[0229] Accurately weigh compound H-53-6 (68 mg, 0.05 mmol) and H-40-1 (47 mg, 0.2 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.2 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain an organic compound (H-62) of about 61 mg, with a yield of 67.8%, MALDI-TOF-MS: 1784.90.

[0230] Example 15: Synthesis of organic compound (H-59)

[0231]

[0232] Synthesis of compound H-59-2:

[0233] Accurately weigh compound H-23-1 (768 mg, 2 mmol) and H-59-1 (2.56 g, 4 mmol) into a 250 mL three-necked flask, add 100 mL of toluene, stir to dissolve, replace nitrogen three times, then add bis(triphenylphosphine)palladium dichloride (42.11 mg, 0.06 mmol), raise the temperature to 100 ° C and react for 1 hour. After the reaction solution is cooled to room temperature, it is poured into water for quenching, extracted with ethyl acetate, concentrated, and purified by column chromatography (PE: EA = 50: 1 (volume ratio) as eluent) to obtain about 1.76 g of compound H-59-2, with a yield of 95.4%. MS: 923.68

[0234] Synthesis of compound H-59-3:

[0235] Accurately weigh the compound triphenylphosphine (1.57 g, 6 mmol) and add it to a 100 mL three-necked flask. Heat to 100 ° C to dissolve it, then add 10 mL of o-dichlorobenzene, then add H-59-2 (1.38 g, 1.5 mmol), heat to 160 ° C, and react for 4 hours. After the reaction solution is cooled to room temperature, pour it into water and stir, extract with dichloromethane, and purify it by column chromatography (PE: EA = 6: 1 (volume ratio) as eluent) to obtain about 916 mg of H-59-3, with a yield of 71.1%. MS: 858.73

[0236] Synthesis of compound H-59-5:

[0237] Accurately weigh compound H-59-3 (859 mg, 1 mmol) and add it to a 100 mL three-necked flask. Dissolve it with 20 ml N, N-dimethylacetamide and add potassium carbonate (552 mg, 4 mmol). Replace nitrogen three times. Stir for 10 minutes and then drop compound H-26-4 (997 mg, 4 mmol). Then raise the temperature to 85 °C and react for 12 hours. Pour the reaction solution into water, extract with ethyl acetate, and purify by column chromatography (petroleum ether as eluent) to obtain about 1.14 g of compound H-59-5, with a yield of 95.3%. MALDI-TOF-MS: 1195.82

[0238] Synthesis of compound H-59-6:

[0239] Accurately weigh compound H-59-5 (957 mg, 0.8 mmol), add it to a 100 mL three-necked flask, dissolve it with 24 ml of anhydrous N, N-dimethylformamide, replace nitrogen three times, cool the temperature to below 0°C with an ice-salt bath, then drop 2.64 ml of phosphorus oxychloride, stir for 30 minutes, heat to 90°C and react for 12 hours. Pour the reaction solution into water to quench, extract with ethyl acetate, and purify by column chromatography (PE:EA=20:1 (volume ratio) as eluent) to obtain about 793 mg of compound H-59-6, with a yield of 79.2%. MALDI-TOF-MS: 1252.28

[0240] Synthesis of organic compound (H-59):

[0241] Accurately weigh compound H-59-6 (125 mg, 0.1 mmol) and H-3-1 (112 mg, 0.4 mmol) and add them to a 100 mL three-necked flask. After adding 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.4 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase, precipitated in methanol, filtered, and dried to obtain about 126 mg of organic compound (H-59), with a yield of 70.7%, MS: 1774.65.

[0242] Example 16: Synthesis of organic compound (H-63)

[0243]

[0244] Synthesis of organic compound (H-63):

[0245] Accurately weigh compound H-59-5 (63 mg, 0.05 mmol) and compound H-36-1 (56 mg, 0.2 mmol) and add them to a 100 mL three-necked flask, add 30 ml of chloroform to dissolve, replace nitrogen 3 times, slowly add 0.2 ml of pyridine, raise the temperature to 85 ° C, and react for 12 hours. After removing most of the solvent by vacuum distillation, the remaining reaction solution was dropped into methanol for precipitation, purified by column chromatography (PE: DCM = 1: 1 (volume ratio) as eluent), concentrated the organic phase and precipitated in methanol, filtered, and dried to obtain about 60.mg of the organic compound (H-63), with a yield of 67.7%, MS: 1773.82.

[0246] Organic solar cell (OPV) device preparation and characterization examples

[0247] The following examples illustrate the preparation, implementation and characterization of the OPV device in the organic electronic device provided by the present invention, but the present invention is not limited to the following examples.

[0248] like Figure 1 As shown, the OPV device structure is as follows: indium tin oxide ITO / PEDOT:PSS / active layer / PDINN / Ag.

[0249] Device Example 1, its preparation steps are as follows:

[0250] 1) ITO substrate cleaning:

[0251] 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.

[0252] 2) Anode buffer layer preparation

[0253] PEDOT:PSS(Clevios TM P VP Al 4083) was evenly spin-coated on ITO at a spin-coating speed of 3000-4000 rpm, and dried at 150° C. for 15 min to obtain an anode buffer layer with a thickness of about 20 nm.

[0254] 3) Preparation of photoactive layer

[0255] In a glove box (inert gas atmosphere), a photoactive layer material solvent ((the total concentration of the donor material and the acceptor material in chlorobenzene is 16.5 mg / mL, and 0.5% by volume of CN is added to the solvent as an additive)) is 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. Among them, the donor material in the photoactive layer material is selected from PM6, the acceptor material is selected from the organic compound (H-2), and the mass ratio of the donor material PM6 to the acceptor material organic compound (H-2) is 1:1.2.

[0256] 4) Preparation of cathode buffer layer

[0257] After thermal annealing on a hot plate at 100°C for 10 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 seconds to obtain a cathode buffer layer.

[0258] 5) Cathode layer preparation

[0259] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer at 400 mbar to form a cathode layer with a thickness of about 100 nm.

[0260] 6) Packaging

[0261] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0262] Device Examples 2-7:

[0263] The preparation methods of device embodiments 2-7 refer to the preparation method of device embodiment 1, except that the choice of photoactive layer receptor material is different. Specifically, the receptor material organic compound (H-2) in device embodiment 1 is replaced by organic compound (H-11), organic compound (H-21), organic compound (H-23), organic compound (H-40), organic compound (H-59) and organic compound (H-62), respectively. See Table 1 for details.

[0264] Device Comparative Example 1

[0265] The preparation method of device comparative example 1 is similar to the preparation method of device example 1, except that the photoactive layer receptor material organic compound (1) is replaced by compound (Ref)

[0266]

[0267] The prepared organic solar 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 1.

[0268] Table 1

[0269] Device Embodiment Photoactive layer receptor materials Photoelectric conversion efficiency (%) Device Example 1 Organic compounds (H-2) 27.96 Device Example 2 Organic compounds (H-11) 28.51 Device Example 3 Organic compounds (H-21) 25.19 Device Example 4 Organic compounds (H-23) 25.74 Device Example 5 Organic compounds (H-40) 26.25 Device Example 6 Organic compounds (H-59) 27.28 Device Example 7 Organic compounds (H-62) 25.32 Device Comparative Example 1 Organic compounds (Ref) 21.80

[0270] It can be seen from the data in Table 1 that when the alkoxy-substituted organic compound according to the present invention is used as an acceptor material in an organic solar cell device, the photoelectric conversion efficiency is greatly improved under indoor lighting conditions compared to the device comparative example 1. The reason is that when the alkoxy-substituted organic compound protected by the present invention is used in an organic solar cell device, it has a more suitable energy level and molecular morphology, thereby showing better photoelectric performance under indoor light.

[0271] 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 alkoxy-substituted organic compound, characterized in that: The alkoxy-substituted organic compound has a structure as shown in the general formula (I): in: Each occurrence of Z is independently selected from O, S or Se; Each occurrence of R1 is independently selected from a straight-chain alkyl group having 1-30 C atoms, a branched or cyclic alkyl group having 3-30 C atoms, an aromatic group having 6-20 carbon atoms, a heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups; Each occurrence of R2 is independently selected from a linear alkoxy group having 1 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a * Substituted aromatic groups having 6 to 20 carbon atoms, or one or more R * Substituted heteroaromatic groups having 5 to 20 ring atoms; R * Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1 to 20 carbon atoms, branched-chain alkyl having 3 to 20 carbon atoms, straight-chain alkoxy having 1 to 20 carbon atoms, branched-chain alkoxy having 3 to 20 carbon atoms, straight-chain alkylthio having 1 to 20 carbon atoms, branched-chain alkylthio having 3 to 20 carbon atoms, or a group formed by a combination of the above groups; and at least one R * is selected from a linear alkoxy group having 1 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms; Each occurrence of M is independently selected from O or C(CN)2; Each occurrence of R3 and R4 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a group formed by a combination of the above groups; Ar1 is selected from unsubstituted or substituted with one or more R # Substituted heteroaromatic groups having 5 to 30 ring atoms; R # Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, cyano, nitro, straight-chain alkyl having 1-20 carbon atoms, branched or cyclic alkyl having 3-20 carbon atoms, straight-chain alkoxy having 1-20 carbon atoms, branched or cyclic alkoxy having 3-20 carbon atoms, straight-chain alkylthio having 1-20 carbon atoms, branched or cyclic alkylthio having 3-20 carbon atoms, aromatic group having 6-20 carbon atoms, heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups.

2. The alkoxy-substituted organic compound according to claim 1, characterized in that: The alkoxy-substituted organic compound has a structure as shown in the general formula (II-1) or the general formula (II-2):

3. The alkoxy-substituted organic compound according to claim 2, characterized in that: The alkoxy-substituted organic compound has a structure as shown in the general formula (III-1), the general formula (III-2), the general formula (III-3), or the general formula (III-4): in: R5, at each occurrence, is independently selected from a straight chain alkyl group having 1-20 C atoms, or a branched chain alkyl group having 3-20 C atoms; Ar2, at each occurrence, is independently selected from an aromatic group having 6-10 carbon atoms, or a heteroaromatic group having 5-10 ring atoms; Each occurrence of R6 is independently selected from a straight chain alkyl group having 1-20 C atoms, or a branched chain alkyl group having 3-20 C atoms.

4. The alkoxy-substituted organic compound according to claim 3, characterized in that: Ar2, at each occurrence, is independently selected from phenyl, naphthyl, thienyl, furanyl, stanphenyl, or thienothiphenyl.

5. The alkoxy-substituted organic compound according to claim 1, characterized in that: Each occurrence of R1 is independently selected from straight chain alkyl having 1-20 C atoms, branched chain alkyl having 3-20 C atoms.

6. The alkoxy-substituted organic compound according to any one of claims 1 to 3, characterized in that: Ar1 is selected from any of the following groups: in: W is selected from O, S, Se or NR7; Each occurrence of X is independently selected from CR8 or N; R7, at each occurrence, is independently selected from a straight chain alkyl group having 1 to 20 C atoms, or a branched chain alkyl group having 3 to 20 C atoms; Each occurrence of R8 is independently selected from -H, -D, -F, -Cl, -Br, -I, cyano, nitro, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched or 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; # indicates a fusion site, which is selected from a C atom.

7. The alkoxy-substituted organic compound according to claim 6, characterized in that: The Ar1 is selected from any of the following groups:

8. The alkoxy-substituted organic compound according to claim 1, characterized in that: The alkoxy-substituted organic compound is selected from the following structures:

9. A mixture, characterized in that: The mixture comprises the alkoxy-substituted organic compound according to any one of claims 1 to 8, and at least another organic functional material.

10. An organic solar cell, comprising at least an anode, a cathode and a photoactive layer located between the anode and the cathode, characterized in that: The photoactive layer comprises the alkoxy-substituted organic compound according to any one of claims 1 to 8 or the mixture according to claim 9 .

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