An organic compound containing an ethylene glycol chain and use thereof

Abstract

The present application relates to the field of organic photovoltaics, and particularly relates to an organic compound containing a glycol chain and application thereof. The present application relates to an organic compound containing a glycol chain as shown in general formula (I), by limiting the N-connected glycol-containing substituent group, thereby improving the photoelectric performance of the compound, introducing it into a binary device as a guest acceptor material, improving the solubility of the material while effectively improving the performance of the device.

Description

Technical Field

[0001] This invention relates to the field of organic photovoltaics, and more specifically to an organic compound containing an ethylene glycol chain and its applications. Technical Background

[0002] Organic photovoltaics (OPPs) exhibit immense promise for applications in wearable electronics and building-integrated devices due to their lightweight, flexibility, semi-transparency, and the ability to fabricate large-area devices through solution processing. Compared to inorganic semiconductors, OPPs typically have lower dielectric constants. The Frenkel excitons generated after photon absorption are bound by Coulomb forces and cannot directly dissociate into free charges. In 1995, Heeger et al. proposed the concept of a "bulk heterojunction," where donor and acceptor materials are thoroughly mixed throughout the active layer. This provides numerous donor / acceptor interfaces for photogenerated exciton dissociation and forms a continuously interpenetrating donor / acceptor phase-separated structure for efficient charge transport. Over the past few decades, researchers have conducted extensive work and achieved breakthroughs in novel donor and acceptor materials and device engineering to improve the photoelectric conversion efficiency of OPPs.

[0003] For binary batteries containing only electron donor and electron acceptor materials, the ability to effectively balance the complementarity of light absorption capabilities and the matching of frontier orbital energy levels significantly limits further improvements in photoelectric conversion efficiency. Therefore, ternary batteries, fabricated by introducing a suitable third component, have attracted widespread attention in the organic photovoltaic field. The introduction of a suitable third component can have multiple benefits. First, the third component can effectively expand the spectral response range of the material system and accelerate charge transfer by enabling cascaded energy level arrangements among the three materials. More importantly, the third component can regulate the microstructure morphology of the active layer, optimizing the phase separation, arrangement, and interpenetrating network structure of the donor and acceptor materials, thereby facilitating exciton diffusion and charge transport. Patent CN113880862A developed a non-fullerene acceptor material with synergistic assembly characteristics, which was used as a third component in the PM6:Y6 system to improve its crystallinity and solution processing properties.

[0004] Acceptor materials containing polar ethylene glycol chains can modulate the intermolecular interactions of the active layer. However, current research on the application of ethylene glycol chains in organic photovoltaic acceptor materials is scarce and limited in variety. Further development of novel acceptor materials containing ethylene glycol side chains to enrich the structural diversity of such acceptor materials and achieve continuous improvement in the optoelectronic performance of devices is of great significance for promoting the technological development and industrial application of organic photovoltaic devices. Summary of the Invention

[0005] Based on this, the purpose of this application is to develop a novel organic compound containing an ethylene glycol chain, thereby improving the photoelectric properties of the compound by defining the ethylene glycol-containing substituent groups connected to N, and introducing it as a guest acceptor material into binary devices, thereby improving the solubility of the material and effectively enhancing the device performance.

[0006] The first aspect of the present invention provides an organic compound containing an ethylene glycol chain, having a structure as shown in general formula (I):

[0007] (I)

[0008] in:

[0009] Y is selected from S or Se;

[0010] Each time Z appears, it is independently selected from S or Se;

[0011] Each time R1 appears, it is independently selected from... ;

[0012] Each time R3 appears, it is independently selected from a straight-chain alkyl group having 1-20 carbon atoms, either substituted or unsubstituted, or a branched alkyl group having 3-20 carbon atoms, either substituted or unsubstituted.

[0013] Each time R4 appears, it is selected independently. ;

[0014] Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-10 carbon atoms, branched alkyl groups having 3-10 carbon atoms, cycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms.

[0015] m1 is selected from any integer from 0 to 5; m2 is selected from any integer from 1 to 5;

[0016] Each time R2 appears, it is independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl with 1-20 carbon atoms, substituted or unsubstituted branched alkyl with 3-20 carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 carbon atoms, substituted or unsubstituted straight-chain alkoxy with 1-20 carbon atoms, substituted or unsubstituted branched alkoxy with 3-20 carbon atoms, substituted or unsubstituted straight-chain alkathio with 1-20 carbon atoms, substituted or unsubstituted branched alkathio with 3-20 carbon atoms, substituted or unsubstituted aromatic group with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group with 5-20 cyclic atoms;

[0017] Each time M appears, it is independently selected from O or C(CN)2;

[0018] Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms;

[0019] The term "substituted or unsubstituted" indicates that the defined group is not substituted, or is substituted by one or more substituents R, wherein each substituent R is independently selected from -D, halogen, cyano, nitro, straight-chain alkyl having 1-30 carbon atoms, branched alkyl having 3-30 carbon atoms, cycloalkyl having 3-30 carbon atoms, straight-chain alkoxy having 1-30 carbon atoms, branched alkoxy having 3-30 carbon atoms, straight-chain alkylthio having 1-30 carbon atoms, branched alkylthio having 3-30 carbon atoms, aromatic group having 6-20 carbon atoms, and heteroaromatic group having 5-20 cyclic atoms, or a combination of at least two of these.

[0020] In an alternative embodiment, m1 is selected from 0, 1, or 2.

[0021] In an alternative embodiment, m2 is selected from 0, 1, 2 or 3.

[0022] Furthermore, each occurrence of R3 is independently selected from the occurrence of R. a A straight-chain alkyl group, substituted or unsubstituted, having 1-16 carbon atoms; the R a Selected from , where: R 6 Each occurrence is independently selected from -D, halogen, cyano, straight-chain alkyl with 1-6 carbon atoms, or branched alkyl with 3-6 carbon atoms; m3 is selected from any integer from 0 to 5; * indicates a linking site.

[0023] In a particular embodiment, m3 is selected from 0 or 1.

[0024] In a specific embodiment, each occurrence of R3 is independently selected from any of the following groups:

[0025] .

[0026] In an optional embodiment, each occurrence of R5 is independently selected from straight-chain alkyl groups having 1-6 carbon atoms, branched alkyl groups having 3-6 carbon atoms, cycloalkyl groups having 3-6 carbon atoms, and R... b Substituted or unsubstituted aromatic groups having 6-10 carbon atoms, or those modified by R b Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms; said R b Each occurrence is independently selected from -D, halogen, cyano, straight-chain alkyl with 1-6 carbon atoms, or branched alkyl with 3-6 carbon atoms.

[0027] Furthermore, each occurrence of R5 is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclohexyl, and methyl ethyl. b Substituted or unsubstituted phenyl, R b Substituted or unsubstituted pyridinyl groups, or those modified by R b Substituted or unsubstituted thiophene group.

[0028] In a specific embodiment, each occurrence of R1 is independently selected from any of the following groups:

[0029]

[0030]

[0031]

[0032]

[0033] .

[0034] In an optional embodiment, each occurrence of R2 is independently selected from -H, -D, straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, cycloalkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, and R2. c Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R c Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; said R c Each occurrence is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, cycloalkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, or branched alkylthio groups having 3-20 carbon atoms.

[0035] In a specific embodiment, R2 is selected from -H, -D, or any of the following structures:

[0036] .

[0037] In an alternative embodiment, the Selected from The Selected from .

[0038] Furthermore, Ar1 and Ar2 are independently selected from R d The substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R d Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; said R d Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CN, -CF3, straight-chain alkyl with 1-10 carbon atoms, branched alkyl with 3-10 carbon atoms, straight-chain alkoxy with 1-10 carbon atoms, or branched alkoxy with 3-10 carbon atoms.

[0039] Furthermore, Ar1 and Ar2 are independently selected from R d The substituted or unsubstituted phenyl group, or the phenyl group with R d Substituted or unsubstituted naphthyl groups.

[0040] Furthermore, the aforementioned , Independently selected from any of the following groups, but not limited to:

[0041]

[0042]

[0043] .

[0044] In one specific embodiment, the organic compound containing an ethylene glycol chain according to the present invention is selected from, but not limited to, the following structures:

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062] .

[0063] A second aspect of the invention relates to a mixture comprising an organic compound containing an ethylene glycol chain as described in the first aspect.

[0064] Further, the mixture comprises a first active layer receptor material and a second active layer receptor material, wherein the mass ratio of the first active layer receptor material to the second active layer material is selected from 1:0.01 to 1:0.3; the second active layer material is selected from organic compounds containing ethylene glycol chains as described in the first aspect.

[0065] Furthermore, the mass ratio of the first active layer receptor material to the second active layer material is selected from 1:0.1 to 1:0.3.

[0066] The first active layer material is preferably selected from Y-type receptor-based materials, including but not limited to: Y6, L8-BO, L8-BO-X, BTP-eC9, N3, N4, Y6-O, HDO-4Cl, BTP-H2, PY-IT, etc.

[0067] Furthermore, the mixture also contains an active layer donor material.

[0068] Preferably, the photoactive layer donor material is selected from polymer donor materials. The polymer donor material may be selected from polythiophene material systems, such as P3AT, P3HT, P3OT, P3DDT, etc.; fluorene-containing polymer material systems, such as PF8BT, etc.; novel structural narrow bandgap polymer material systems, such as benzodithiophene (BDT), benzothiadiazoles (BT, BBT), quinoxalines (QU, PQ), pyrazines (TP, PQ), and copolymers with electron-rich groups (such as thiophene derivatives), such as PM6, PM7, PBDB-T, D18, D18-Cl, PTQ10, PTQ11, PBQx-TCl, PBQx-TF, PB2, etc., but is not limited to these.

[0069] Further references can be found regarding the selection of acceptor materials for the active layer: Chem. Rev. 2022, 122, 18, 14180–14274.

[0070] A third aspect of the present invention relates to a composition comprising an organic compound containing an ethylene glycol chain as described in the first aspect, or a mixture as described in the second aspect, and at least one organic solvent.

[0071] The organic solvent is selected from, but not limited to: tetrahydronaphthalene, 1,5-dimethyltetrahydrofuran, methyltetrahydrofuran, decahydronaphthalene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,4-dimethylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, acetophenone, diphenyl ether, 2-methylthiophene, 3-methylthiophene, monochloromethane, dichloromethane, chloroform, dichloroethylene, trichloroethylene, 1,2-trichlorotrifluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2 One or a mixture of two or more of the following: 4-dimethylanisole, 1-methylnaphthalene, morpholine, 1,4-dioxane, N-methylpyrrolidone, acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, carbon disulfide, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, indane, methyl benzoate, ethyl benzoate, acetonitrile, and hexamethylphosphoramide.

[0072] Furthermore, the composition may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives may be selected from, but are 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.

[0073] The fourth aspect of the present invention relates to an organic photovoltaic device comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, the photoactive layer comprising an organic compound containing an ethylene glycol chain as described in the first aspect, or a mixture as described in the second aspect, or prepared from a composition described in the third aspect.

[0074] In one embodiment, the photoactive layer comprises a photoactive layer donor material and a photoactive layer acceptor material, wherein the photoactive layer acceptor material comprises an organic compound containing an ethylene glycol chain as described in the first aspect.

[0075] Furthermore, the selection of donor and acceptor materials for the photoactive layer is as described above.

[0076] The method for preparing the photoactive layer material solution is as follows: the photoactive layer donor material and acceptor material are dissolved in an organic solvent at a certain mass ratio, and the mixture is stirred until fully dissolved to obtain the photoactive layer solution.

[0077] The above solution is used to prepare the photoactive layer by printing or coating methods. These printing or coating methods can include, but are not limited to, inkjet printing, gravure printing, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, and slot-loaded extrusion coating. Slot-loaded coating, spin coating, and inkjet printing are preferred.

[0078] The preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:0.8 to 1:1.5; further, the preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:1 to 1:1.5; the preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:1 to 1:1.2.

[0079] 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.

[0080] At least one of the anode and cathode is transparent or translucent to facilitate light incidence. The material used to fabricate 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 pastes, graphene, carbon nanotubes; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; and conductive polymers such as PEDOT:PSS, polypyrrole, and polyaniline; or composite structures having multiple layers of electrode materials, such as metal / ITO (or ITO / metal), and ITO / metal / ITO, AZO / metal / AZO, etc., but not limited to these.

[0081] In one embodiment, the organic photovoltaic device comprises an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode stacked sequentially.

[0082] Preferably, the cathode buffer layer material can be selected from low work function metal complexes, metal oxides, metal salts, etc., such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, PEI-Zn, LiF, titanium oxide (TiO2). x It can be zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be polymer materials, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited to these.

[0083] The anode buffer layer material is selected from PEDOT:PSS and molybdenum oxide (MoO). x ), vanadium oxide (V₂O₅), nickel oxide (NiO), tungsten oxide (WO₂) x Preferably, x is selected from 2 or 3), small molecule self-assembled materials such as 2PACz, MeO-2PACz, etc., but not limited to these.

[0084] It should be noted that, in order to improve the device performance of organic photovoltaics, the organic photovoltaic cell may further include other functional layers, including but not limited to charge blocking layers and charge transport layers.

[0085] Furthermore, the organic photovoltaic device also includes a substrate. In one embodiment, the substrate is disposed on the anode side and away from the photoactive layer. In another embodiment, the substrate is disposed on the cathode side and away from the photoactive layer.

[0086] In one embodiment, a substrate with excellent transparency, surface smoothness, ease of handling, and water resistance can be used as the substrate. Specifically, a glass substrate, a thin-film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include films in the form of single or multiple layers, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), parylene, etc., but is not limited to these, and substrates commonly used in organic solar cells may also be used.

[0087] The organic photovoltaic devices described in this invention are mainly used in indoor photovoltaics, wearable devices, smart IoT, smart homes, smart agriculture, building photovoltaics, new energy vehicles and other fields.

[0088] The beneficial effects of this invention are:

[0089] This invention develops an organic compound containing an ethylene glycol chain, as shown in general formula (I), wherein the R1 group attached to N on the inner side of the molecule is selected from a branched structure containing an ethylene glycol chain. On the one hand, by introducing a strongly polar ethylene glycol side chain, the dipole moment of the molecule is increased, thereby enhancing the dielectric properties of the molecule, reducing the exciton binding energy, and improving the voltage and current of the device. Furthermore, by introducing the ethylene glycol side chain, it can form strong non-covalent interactions with other molecules in the active layer, thereby regulating the molecular stacking of the active layer to achieve morphology optimization and enhance intramolecular charge transfer. On the other hand, the branched structure can improve the crystal structure, molecular stacking, and solubility of the compound, allowing the organic compound containing the ethylene glycol chain to better form an "alloy state" with the host and acceptor materials and form a more suitable molecular stacking, promoting exciton separation and transport. Based on this, when introduced as a third component into a suitable binary system, a photoelectric conversion efficiency exceeding 20.3% can be achieved. Attached Figure Description

[0090] Figure 1 This is a schematic diagram of the device structure in an embodiment of the present invention. Detailed Implementation

[0091] To make the objectives, technical solutions, and effects of this application clearer and more explicit, the following provides a further detailed description of this application. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention without inventive effort are within the scope of protection of this invention.

[0092] The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These 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 connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: 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, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").

[0093] In this invention, organic photovoltaic devices, organic solar cells, OPV, and OSC have the same meaning and can be used interchangeably.

[0094] In this invention, the terms "photoactive layer" and "active layer" have the same meaning and can be used interchangeably.

[0095] In this invention, when the same group contains multiple substituents with the same symbol, the substituents can be the same as or different from each other, for example... The six Rs on the benzene ring can be the same or different from each other.

[0096] In this invention, "substitution" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0097] In this invention, "halogen" refers to -F, -Cl, -Br, and -I.

[0098] In this invention, "ring atom number" refers to the number of atoms in the ring itself of a structural compound (e.g., monocyclic compound, fused-ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. In aromatic groups, the ring atom number is the same as the carbon atom number; in heteroaromatic groups, the ring atom number is the carbon atom number plus the heteroatom number; for example, the ring atom number of a benzene ring is 6, the ring atom number of a naphthalene ring is 10, the ring atom number of a quinoline ring is 10, the ring atom number of a thiophene group is 5, and the ring atom number of a thiophene is 8.

[0099] In this invention, "aromatic group" refers to any optional functional group or substituent derived from an aromatic carbide ring. The aromatic group can be a monocyclic aryl (e.g., phenyl) or a polycyclic aryl; in other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated by carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise stated, two or more aromatic groups conjugated by carbon-carbon bonds can also be considered as aromatic groups in this application. Preferably, the aromatic group is selected from aromatic groups having 6-20 carbon atoms; further, it is selected from aromatic groups having 6-10 carbon atoms; the aromatic group includes, but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluoranthracene, and their derivatives.

[0100] In this invention, a "heteroaromatic group" refers to a heteroaromatic ring or its derivative containing one, two, three, four, five, six or more heteroatoms, wherein the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl or a polycyclic heteroaryl. The term "heteroaromatic group" as used herein also includes groups formed by the fusion of one or more heteroaromatic groups with one or more aromatic rings, aliphatic rings or heterocycles. Preferably, the heteroaromatic group is selected from those having 5-20 ring atoms; more preferably, it is selected from those having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to: thiophene, furanyl, pyrrolyl, diazolyl, triazolyl, imidazole, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridineyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, benzothiophene, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrryl, thienopyrryl, thienothiophene, furanol, furanol, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazanaphthyl, phenanthridine, primidyl, quinazolinone, dibenzothiophene, dibenzofuranyl, carbazole, phenazinyl and their derivatives.

[0101] In this invention, the alkyl group comprises straight-chain alkyl, branched-chain alkyl, cyclic alkyl, and combinations thereof. The straight-chain alkyl group may have 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6 carbon atoms. The branched-chain alkyl group may have 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6 carbon atoms. The cyclic alkyl group may have 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6 carbon atoms. Non-limiting examples of straight-chain alkyl groups include methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), and n-pentyl (-C5H9). 11 ), n-hexyl (-C6H) 13 ), heptyl (-C7H) 15 ), octyl (-C8H) 17 ), non-nonyl (-C9H) 19 -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 33Non-limiting examples of branched alkyl groups include: isopropyl, branched alkyl groups containing 4 carbon atoms, branched alkyl groups containing 5 carbon atoms, branched alkyl groups containing 6 carbon atoms, branched alkyl groups containing 7 carbon atoms, branched alkyl groups containing 8 carbon atoms, branched alkyl groups containing 9 carbon atoms, branched alkyl groups containing 10 carbon atoms, branched alkyl groups containing 11 carbon atoms, branched alkyl groups containing 12 carbon atoms, branched alkyl groups containing 13 carbon atoms, branched alkyl groups containing 14 carbon atoms, branched alkyl groups containing 15 carbon atoms, and branched alkyl groups containing 16 carbon atoms. Non-limiting examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0102] The term "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above that is attached to other groups via an oxygen atom. The straight-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0103] The term "alkoxythio" refers to a group with the structure "-S-alkyl", that is, an alkyl group as defined above that is attached to other groups via a sulfur atom. The straight-chain alkoxythio group indicates that the alkyl group in the "-S-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxythio group indicates that the alkyl group in the "-S-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0104] In this invention, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0105] In this invention, the phrase "independently selected" means that when one or more groups appear simultaneously and in multiple places in the compound, they are all independently selected and can be the same or different.

[0106] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0107] In describing the structural elements of the present invention, the terms "comprising" or "including" or similar terms used in the present invention mean that the device or material preceding the word covers the device or material listed after the word and its equivalents, but does not exclude other devices or materials.

[0108] In the description of this invention, it should be understood that the terms "upper," "lower," "between layers," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship commonly used when organic solar cell devices are in use, or the orientation or positional relationship commonly understood by those skilled in the art. They are only used to facilitate the description of this invention and to simplify the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting this invention.

[0109] The terms “combinations thereof,” “any combination thereof,” “any combination thereof,” and “combination” used in this invention include all suitable combinations of any two, any three, or any three or more groups listed.

[0110] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0111] In this invention, "optionally," "optionally," and "optional" mean that they are optional, that is, they are selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent.

[0112] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0113] Organic compound synthesis examples

[0114] The following examples are provided to facilitate a better understanding of the disclosure of this invention, but are not intended to limit it in any way. Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials and reagents used are, unless otherwise specified, prior art and commercially available. Wherein -Ph represents phenyl.

[0115] Synthesis of intermediate L-1

[0116]

[0117] Synthesis of compound 1-1:

[0118] Under a nitrogen atmosphere, NaH (60% dispersed in mineral oil) (3.6 g, 90.0 mmol) was dissolved in anhydrous THF (100 mL). 2-(chloromethyl)but-1-ene (3.1 g, 30.0 mmol) was added dropwise at 0 °C for 10 min, followed by the addition of 2-methoxyethanol (6.84 g, 90.0 mmol), and the reaction was continued at 65 °C for 12 h. After cooling to room temperature, the reaction was quenched with deionized water, and the reaction was extracted with dichloromethane and saturated brine. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / ethyl acetate (v / v = 3 / 1) to give compound 1-1 (3.67 g, yield 84.6%). MS: 144.52.

[0119] Synthesis of compounds 1-2:

[0120] Compound 1-1 (3.5 g, 24.0 mmol) was dissolved in anhydrous THF (80 mL) under a nitrogen atmosphere. BH3·THF (30 mL) was added dropwise at 0 °C, and the reaction was allowed to proceed to room temperature for 2 h. The reaction was quenched with 3 M sodium hydroxide aqueous solution, followed by the addition of 30% H2O2 aqueous solution (40 mL), and the mixture was stirred at room temperature for 30 min. The reaction was extracted with dichloromethane and saturated potassium carbonate solution, and the organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / ethyl acetate (v / v = 2 / 1) to give compound 1-2 (3.44 g, yield 88.2%). MS: 162.36.

[0121] Synthesis of compound L-1:

[0122] Under a nitrogen atmosphere, compounds 1-2 (3.25 g, 20.0 mmol), PPh3 (6.6 g, 25.0 mmol), and imidazole (1.7 g, 25.0 mmol) were dissolved in dichloromethane (100 mL). Solid iodine (6.4 g, 25.0 mmol) was added at 0 °C, and the reaction was allowed to proceed to room temperature for 4 h. The reaction was quenched with saturated sodium sulfite solution, and the reaction was extracted with saturated brine and dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / ethyl acetate (v / v = 3 / 1) to give compound L-1 (4.21 g, yield 77.2%). MS: 272.84.

[0123] Synthesis of intermediate L-2

[0124]

[0125] Synthesis of compound 2-1:

[0126] Under a nitrogen atmosphere, NaH (60% dispersed in mineral oil) (1.8 g, 45.0 mmol) was dissolved in anhydrous THF (50 mL). (2-(chloromethyl)allyl)benzene (2.5 g, 15.0 mmol) was added dropwise at 0 °C for 10 min, followed by the addition of 2-methoxyethanol (3.42 g, 45.0 mmol), and the reaction was continued at 65 °C for 12 h. Subsequent synthetic reactions followed the synthesis of compound 1-1, yielding compound 2-1 (2.52 g, yield 81.3%). MS: 206.59.

[0127] Synthesis of compound 2-2:

[0128] Compound 2-1 (2.48 g, 12.0 mmol) was dissolved in anhydrous THF (40 mL) under a nitrogen atmosphere. BH3·THF (15 mL) was added dropwise at 0 °C, and the reaction was allowed to proceed to room temperature for 2 h. The reaction was quenched with 3 M sodium hydroxide aqueous solution, followed by the addition of 30% H2O2 aqueous solution (20 mL), and the mixture was stirred at room temperature for 30 min. Subsequent synthetic reactions followed the synthesis of compounds 1-2, yielding compound 2-2 (2.26 g, 84.0% yield). MS: 224.27.

[0129] Synthesis of compound L-2:

[0130] Under a nitrogen atmosphere, compound 2-2 (2.24 g, 10.0 mmol), PPh3 (3.3 g, 12.5 mmol), and imidazole (0.85 g, 12.5 mmol) were dissolved in dichloromethane (50 mL). Solid iodine (3.2 g, 12.5 mmol) was added at 0 °C, and the mixture was reacted at room temperature for 4 h. Subsequent synthetic reactions followed the synthesis of compound L-1, yielding compound L-2 (2.53 g, 75.6% yield). MS: 334.61.

[0131] Synthesis of intermediate L-3

[0132]

[0133] Synthesis of compound 3-1:

[0134] Under a nitrogen atmosphere, NaH (60% dispersed in mineral oil) (3.6 g, 90.0 mmol) was dissolved in anhydrous THF (100 mL), and 2-(chloromethyl)hex-1-ene (4.0 g, 30.0 mmol) was added dropwise at 0 °C for 10 min. Then, 2-methoxyethanol (6.84 g, 90.0 mmol) was added dropwise, and the reaction was continued at 65 °C for 12 h. Subsequent synthetic reactions followed the synthesis of compound 1-1, yielding compound 3-1 (4.25 g, yield 82.1%). MS: 172.49.

[0135] Synthesis of compound 3-2:

[0136] Compound 3-1 (4.1 g, 24.0 mmol) was dissolved in anhydrous THF (80 mL) under a nitrogen atmosphere. BH3·THF (30 mL) was added dropwise at 0 °C, and the reaction was allowed to proceed to room temperature for 2 h. The reaction was quenched with 3 M sodium hydroxide aqueous solution, followed by the addition of 30% H2O2 aqueous solution (40 mL), and the mixture was stirred at room temperature for 30 min. Subsequent synthetic reactions followed the synthesis of compounds 1-2, yielding compound 3-2 (4.02 g, 87.8% yield). MS: 190.76.

[0137] Synthesis of compound L-3:

[0138] Under a nitrogen atmosphere, compounds 3-2 (3.8 g, 20.0 mmol), PPh3 (6.6 g, 25.0 mmol), and imidazole (1.7 g, 25.0 mmol) were dissolved in dichloromethane (100 mL). Solid iodine (6.4 g, 25.0 mmol) was added at 0 °C, and the mixture was reacted at room temperature for 4 h. Subsequent synthetic reactions followed the synthesis of compound L-1, yielding compound L-3 (4.79 g, yield 79.7%). MS: 300.52.

[0139] Synthesis of intermediate L-4

[0140]

[0141] Synthesis of compound 4-1:

[0142] Under a nitrogen atmosphere, NaH (60% dispersed in mineral oil) (1.8 g, 45.0 mmol) was dissolved in anhydrous THF (50 mL), and 2-(chloromethyl)oct-1-ene (2.4 g, 15.0 mmol) was added dropwise at 0 °C for 10 min. Then, 2-n-propoxyethanol (4.7 g, 45.0 mmol) was added dropwise, and the reaction was continued at 65 °C for 12 h. Subsequent synthetic reactions followed the synthesis of compound 1-1, yielding compound 4-1 (3.01 g, yield 87.8%). MS: 228.46.

[0143] Synthesis of compound 4-2:

[0144] Compound 4-1 (2.7 g, 12.0 mmol) was dissolved in anhydrous THF (40 mL) under a nitrogen atmosphere. BH3·THF (15 mL) was added dropwise at 0 °C, and the reaction was allowed to proceed to room temperature for 2 h. The reaction was quenched with 3 M sodium hydroxide aqueous solution, followed by the addition of 30% H2O2 aqueous solution (20 mL), and the mixture was stirred at room temperature for 30 min. Subsequent synthetic reactions followed the method for compound 1-2, yielding compound 4-2 (2.54 g, 86.0% yield). MS: 246.07.

[0145] Synthesis of compound L-4:

[0146] Under a nitrogen atmosphere, compound 4-2 (2.46 g, 10.0 mmol), PPh3 (3.3 g, 12.5 mmol), and imidazole (0.85 g, 12.5 mmol) were dissolved in dichloromethane (50 mL). Solid iodine (3.2 g, 12.5 mmol) was added at 0 °C, and the mixture was reacted at room temperature for 4 h. Subsequent synthetic reactions followed the synthesis of compound L-1, yielding compound L-4 (2.47 g, yield 69.4%). MS: 356.15.

[0147] Synthesis of intermediate L-5

[0148]

[0149] Synthesis of compound 5-1:

[0150] Under a nitrogen atmosphere, NaH (60% dispersed in mineral oil) (1.8 g, 45.0 mmol) was dissolved in anhydrous THF (50 mL), and 2-(chloromethyl)oct-1-ene (2.4 g, 15.0 mmol) was added dropwise at 0 °C for 10 min. Then, diethylene glycol monomethyl ether (5.4 g, 45.0 mmol) was added dropwise, and the reaction was continued at 65 °C for 12 h. Subsequent synthetic reactions followed the synthesis of compound 1-1, yielding compound 5-1 (3.14 g, 85.6% yield). MS: 244.67.

[0151] Synthesis of compound 5-2:

[0152] Compound 5-1 (2.9 g, 12.0 mmol) was dissolved in anhydrous THF (40 mL) under a nitrogen atmosphere. BH3·THF (15 mL) was added dropwise at 0 °C, and the reaction was allowed to proceed to room temperature for 2 h. The reaction was quenched with 3 M sodium hydroxide aqueous solution, followed by the addition of 30% H2O2 aqueous solution (20 mL), and the mixture was stirred at room temperature for 30 min. Subsequent synthetic reactions followed the synthesis of compounds 1-2, yielding compound 5-2 (2.52 g, 80.2% yield). MS: 261.99.

[0153] Synthesis of compound L-5:

[0154] Under a nitrogen atmosphere, compound 5-2 (2.4 g, 9.0 mmol), PPh3 (3.0 g, 11.25 mmol), and imidazole (0.77 g, 11.25 mmol) were dissolved in dichloromethane (50 mL). Solid iodine (2.9 g, 11.25 mmol) was added at 0 °C, and the reaction was allowed to proceed to room temperature for 4 h. Subsequent synthetic reactions followed the synthesis of compound L-1, yielding compound L-5 (2.36 g, 70.4% yield). MS: 372.82.

[0155] Synthesis of intermediate L-6

[0156]

[0157] Synthesis of compound 6-1:

[0158] Under a nitrogen atmosphere, NaH (60% dispersed in mineral oil) (1.8 g, 45.0 mmol) was dissolved in anhydrous THF (50 mL). 2-(chloromethyl)hex-1-ene (2.0 g, 15.0 mmol) was added dropwise at 0 °C for 10 min, followed by the addition of 2-phenoxyethanol (6.2 g, 45.0 mmol), and the reaction was continued at 65 °C for 12 h. Subsequent synthetic reactions followed the synthesis of compound 1-1, yielding compound 6-1 (2.89 g, 82.3% yield). MS: 234.21.

[0159] Synthesis of compound 6-2:

[0160] Compound 6-1 (2.8 g, 12.0 mmol) was dissolved in anhydrous THF (40 mL) under a nitrogen atmosphere. BH3·THF (15 mL) was added dropwise at 0 °C, and the reaction was allowed to proceed to room temperature for 2 h. The reaction was quenched with 3 M sodium hydroxide aqueous solution, followed by the addition of 30% H2O2 aqueous solution (20 mL), and the mixture was stirred at room temperature for 30 min. Subsequent synthetic reactions followed the method described for compounds 1-2, yielding compound 6-2 (2.56 g, 84.6% yield). MS: 252.10.

[0161] Synthesis of compound L-6:

[0162] Under a nitrogen atmosphere, compound 6-2 (2.5 g, 10.0 mmol), PPh3 (3.3 g, 12.5 mmol), and imidazole (0.85 g, 12.5 mmol) were dissolved in dichloromethane (50 mL). Solid iodine (3.2 g, 12.5 mmol) was added at 0 °C, and the mixture was reacted at room temperature for 4 h. Subsequent synthetic reactions followed the synthesis of compound L-1, yielding compound L-6 (2.41 g, yield 66.4%). MS: 362.96.

[0163] Synthesis of intermediate L-7

[0164]

[0165] Synthesis of compound 7-1:

[0166] Under a nitrogen atmosphere, NaH (60% dispersed in mineral oil) (1.8 g, 45.0 mmol) was dissolved in anhydrous THF (50 mL). 3-(chloromethyl)hepta-1-ene (2.2 g, 15.0 mmol) was added dropwise at 0 °C for 10 min, followed by the addition of 2-methoxyethanol (3.42 g, 45.0 mmol), and the reaction was continued at 65 °C for 12 h. Subsequent synthetic reactions followed the synthesis of compound 1-1, yielding compound 7-1 (2.38 g, 85.0% yield). MS: 186.75.

[0167] Synthesis of compound 7-2:

[0168] Compound 7-1 (2.2 g, 12.0 mmol) was dissolved in anhydrous THF (40 mL) under a nitrogen atmosphere. BH3·THF (15 mL) was added dropwise at 0 °C, and the reaction was allowed to proceed to room temperature for 2 h. The reaction was quenched with 3 M sodium hydroxide aqueous solution, followed by the addition of 30% H2O2 aqueous solution (20 mL), and the mixture was stirred at room temperature for 30 min. Subsequent synthetic reactions followed the method described for compounds 1-2, yielding compound 7-2 (2.16 g, 88.3% yield). MS: 203.91.

[0169] Synthesis of compound L-7:

[0170] Under a nitrogen atmosphere, compound 7-2 (2.0 g, 10.0 mmol), PPh3 (3.3 g, 12.5 mmol), and imidazole (0.85 g, 12.5 mmol) were dissolved in dichloromethane (50 mL). Solid iodine (3.2 g, 12.5 mmol) was added at 0 °C, and the mixture was reacted at room temperature for 4 h. Subsequent synthetic reactions followed the synthesis of compound L-1, yielding compound L-7 (2.19 g, yield 69.6%). MS: 314.54.

[0171] Synthesis Example 1: Synthesis of Compound (1)

[0172]

[0173] Synthesis of compound 2a:

[0174] Compound 1a (2.3 g, 3.0 mmol), potassium hydroxide (1.0 g, 18.0 mmol), and DMF (20 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-1 (2.0 g, 7.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to obtain compound 2a (2.35 g, 73.6%). MADLI-TOF-MS: 1063.67.

[0175] Synthesis of compound 3a:

[0176] Compound 2a (1.1 g, 1.0 mmol) was dissolved in 1,2-dichloroethane (15 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4.5 mL) and DMF (30 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to obtain compound 3a (670 mg, 59.9%). MADLI-TOF-MS: 1119.28.

[0177] Synthesis of compound (1):

[0178] Under a nitrogen atmosphere, compound 3a (560 mg, 0.5 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (690 mg, 3.0 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) to give compound (1) (486 mg, 63.0%). MADLI-TOF-MS: 1543.72.

[0179] Synthesis Example 2: Synthesis of Compound (7)

[0180]

[0181] Synthesis of compound 2b:

[0182] Compound 1a (2.3 g, 3.0 mmol), potassium hydroxide (1.0 g, 18.0 mmol), and DMF (20 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-2 (2.5 g, 7.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2b (2.75 g, 77.2%). MADLI-TOF-MS: 1187.41.

[0183] Synthesis of compound 3b:

[0184] Compound 2b (1.2 g, 1.0 mmol) was dissolved in 1,2-dichloroethane (15 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4.5 mL) and DMF (30 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound 3b (835 mg, 67.1%). MADLI-TOF-MS: 1243.87.

[0185] Synthesis of compound (7):

[0186] Under a nitrogen atmosphere, compound 3b (622 mg, 0.5 mmol), 5,6-difluoro-3-(dicyanomethylene)indophenone (115 mg, 0.5 mmol), and 2-(6,7-difluoro-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthyl-1-yl)malononitrile (140 mg, 0.5 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) to give compound (7) (307 mg, 35.7%). MADLI-TOF-MS: 1718.34.

[0187] Synthesis Example 3: Synthesis of Compound (10)

[0188]

[0189] Synthesis of compound 2c:

[0190] Compound 1c (2.2 g, 3.0 mmol), potassium hydroxide (1.0 g, 18.0 mmol), and DMF (20 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-1 (2.0 g, 7.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to obtain compound 2c (2.18 g, 70.2%). MADLI-TOF-MS: 1035.71.

[0191] Synthesis of compound 3c:

[0192] Compound 2c (1.0 g, 1.0 mmol) was dissolved in 1,2-dichloroethane (15 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4.5 mL) and DMF (30 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound 3c (712 mg, 65.2%). MADLI-TOF-MS: 1091.29.

[0193] Synthesis of compound (10):

[0194] Compound 3c (546 mg, 0.5 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (690 mg, 3.0 mmol) were dissolved in chloroform (40 mL) under a nitrogen atmosphere. 4 mL of pyridine was added, and the mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v = 1 / 1) to give compound (10) (466 mg, 61.5%). MADLI-TOF-MS: 1516.42.

[0195] Synthesis Example 4: Synthesis of Compound (16)

[0196]

[0197] Synthesis of compound 2d:

[0198] Compound 1a (2.3 g, 3.0 mmol), potassium hydroxide (1.0 g, 18.0 mmol), and DMF (20 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-3 (2.2 g, 7.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2d (2.57 g, 76.5%). MADLI-TOF-MS: 1119.84.

[0199] Synthesis of compound 3d:

[0200] Compound 2d (2.24 g, 2.0 mmol) was dissolved in 1,2-dichloroethane (30 mL) under a nitrogen atmosphere, and anhydrous POCl3 (9 mL) and DMF (50 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound 3d (1.60 g, 67.9%). MADLI-TOF-MS: 1175.38.

[0201] Synthesis of compound (16):

[0202] Compound 3d (588 mg, 0.5 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (690 mg, 3.0 mmol) were dissolved in chloroform (40 mL) under a nitrogen atmosphere, and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (16) (498 mg, 62.3%). MADLI-TOF-MS: 1599.57.

[0203] Synthesis Example 5: Synthesis of Compound (17)

[0204]

[0205] Compound 3d (588 mg, 0.5 mmol) and 5,6-dichloro-3-(dicyanomethylene)indophenone (789 mg, 3.0 mmol) were dissolved in chloroform (40 mL) under a nitrogen atmosphere, and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (17) (526 mg, 63.1%). MADLI-TOF-MS: 1666.09.

[0206] Synthesis Example 6: Synthesis of Compound (24)

[0207]

[0208] Synthesis of compound 2e:

[0209] Compound 1c (747 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-3 (750 mg, 2.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2e (843 mg, 77.2%). MADLI-TOF-MS: 1091.64.

[0210] Synthesis of compound 3e:

[0211] Compound 2e (764 mg, 0.7 mmol) was dissolved in 1,2-dichloroethane (10 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4 mL) and DMF (20 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as eluent to obtain compound 3e (546 mg, 68.0%). MADLI-TOF-MS: 1147.25.

[0212] Synthesis of compound (24):

[0213] Under a nitrogen atmosphere, compound 3e (459 mg, 0.4 mmol) and 2-(6,7-difluoro-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphth-1-yl)malononitrile (673 mg, 2.4 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (24) (398 mg, 59.5%). MADLI-TOF-MS: 1672.08.

[0214] Synthesis Example 7: Synthesis of Compound (26)

[0215]

[0216] Synthesis of compound 2f:

[0217] Compound 1a (1.6 g, 2.0 mmol), potassium hydroxide (673.3 mg, 12.0 mmol), and DMF (20 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-4 (1.78 g, 5.0 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2f (1.71 g, 69.4%). MADLI-TOF-MS: 1232.15.

[0218] Synthesis of compound 3f:

[0219] Compound 2f (1.23 g, 1.0 mmol) was dissolved in 1,2-dichloroethane (15 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4.5 mL) and DMF (30 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to obtain compound 3f (838 mg, 65.1%). MADLI-TOF-MS: 1287.69.

[0220] Synthesis of compound (26):

[0221] Compound 3f (644 mg, 0.5 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (690 mg, 3.0 mmol) were dissolved in chloroform (40 mL) under a nitrogen atmosphere, and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (26) (589 mg, 68.8%). MADLI-TOF-MS: 1712.22.

[0222] Synthesis Example 8: Synthesis of Compound (32)

[0223]

[0224] Synthesis of compound 2g:

[0225] Compound 1a (775 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-5 (745 mg, 2.0 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) to give 2 g (952 mg, 75.3%) of the compound. MADLI-TOF-MS: 1263.55.

[0226] Synthesis of compound 3g:

[0227] Under a nitrogen atmosphere, 2 g (884 mg, 0.7 mmol) of the compound was dissolved in 1,2-dichloroethane (10 mL), and anhydrous POCl3 (4 mL) and DMF (20 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give 3 g (685 mg, 74.2%) of the compound. MADLI-TOF-MS: 1319.37.

[0228] Synthesis of compound (32):

[0229] Under a nitrogen atmosphere, 3 g (528 mg, 0.4 mmol) of compound and 5,6-difluoro-3-(dicyanomethylene)indophenone (552 mg, 2.4 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (32) (495 mg, 70.9%). MADLI-TOF-MS: 1744.15.

[0230] Synthesis Example 9: Synthesis of Compound (33)

[0231]

[0232] Synthesis of compound 2h:

[0233] Compound 1h (822 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-5 (744.6 mg, 2.0 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2h (937 mg, 71.5%). MADLI-TOF-MS: 1310.90.

[0234] Synthesis of compound 3h:

[0235] Compound 2h (918 mg, 0.7 mmol) was dissolved in 1,2-dichloroethane (10 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4 mL) and DMF (20 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as eluent to give compound 3h (576 mg, 60.2%). MADLI-TOF-MS: 1366.73.

[0236] Synthesis of compound (33):

[0237] Under a nitrogen atmosphere, compound 3h (547 mg, 0.4 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (552 mg, 2.4 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (33) (534 mg, 74.5%). MADLI-TOF-MS: 1791.26.

[0238] Synthesis Example 10: Synthesis of Compound (36)

[0239]

[0240] Synthesis of compound 2i:

[0241] Compound 1i (596 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-3 (750 mg, 2.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2i (691 mg, 73.5%). MS: 940.66.

[0242] Synthesis of compound 3i:

[0243] Under a nitrogen atmosphere, compound 2i (658 mg, 0.7 mmol), (4-(2-ethylhexyl)thiophen-2-yl)tributyltinane (1.0 g, 2.1 mmol), and Pd(PPh3)4 (40.4 mg, 0.035 mmol) were added to a reaction flask and heated to reflux for 12 h using toluene as solvent. After cooling to room temperature, the reaction was extracted with saturated brine and dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) to give compound 3i (617 mg, 75.2%). MADLI-TOF-MS: 1171.34.

[0244] Synthesis of compound 4i:

[0245] Compound 3i (586 mg, 0.5 mmol) was dissolved in 1,2-dichloroethane (10 mL) under a nitrogen atmosphere, and anhydrous POCl3 (3 mL) and DMF (15 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to obtain compound 4i (375 mg, 61.1%). MADLI-TOF-MS: 1227.56.

[0246] Synthesis of compound (36):

[0247] Compound 4i (368 mg, 0.3 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (414 mg, 1.8 mmol) were dissolved in chloroform (30 mL) under a nitrogen atmosphere, and 3 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (36) (314 mg, 63.4%). MADLI-TOF-MS: 1652.49.

[0248] Synthesis Example 11: Synthesis of Compound (39)

[0249]

[0250] Synthesis of compound 2j:

[0251] Compound 1a (775 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-6 (906 mg, 2.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2j (957 mg, 77.0%). MADLI-TOF-MS: 1243.55.

[0252] Synthesis of compound 3j:

[0253] Compound 2j (870 mg, 0.7 mmol) was dissolved in 1,2-dichloroethane (10 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4 mL) and DMF (20 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to obtain compound 3j (645 mg, 70.9%). MADLI-TOF-MS: 1299.74.

[0254] Synthesis of compound (39):

[0255] Compound 3j (520 mg, 0.4 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (552 mg, 2.4 mmol) were dissolved in chloroform (40 mL) under a nitrogen atmosphere. 4 mL of pyridine was added, and the mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v = 1 / 1) as the eluent to give compound (39) (457 mg, 66.2%). MADLI-TOF-MS: 1725.03.

[0256] Synthesis Example 12: Synthesis of Compound (44)

[0257]

[0258] Synthesis of compound 2k:

[0259] Compound 1k (807 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-3 (750 mg, 2.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to obtain compound 2k (896 mg, 77.8%). MADLI-TOF-MS: 1151.20.

[0260] Synthesis of compound 3k:

[0261] Compound 2k (806 mg, 0.7 mmol) was dissolved in 1,2-dichloroethane (10 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4 mL) and DMF (20 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as eluent to give compound 3k (615 mg, 72.7%). MADLI-TOF-MS: 1207.84.

[0262] Synthesis of compound (44):

[0263] Under a nitrogen atmosphere, compound 3k (483 mg, 0.4 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (552 mg, 2.4 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (44) (447 mg, 68.5%). MADLI-TOF-MS: 1631.70.

[0264] Synthesis Example 13: Synthesis of Compound (49)

[0265]

[0266] Synthesis of compound 2l:

[0267] Compound 1k (807 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-5 (744 mg, 2.0 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2l (1013 mg, 78.2%). MADLI-TOF-MS: 1295.88.

[0268] Synthesis of compound 3l:

[0269] Compound 2l (907 mg, 0.7 mmol) was dissolved in 1,2-dichloroethane (10 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4 mL) and DMF (20 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound 3l (635 mg, 67.1%). MADLI-TOF-MS: 1352.10.

[0270] Synthesis of compound (49):

[0271] Under a nitrogen atmosphere, compound 3l (541 mg, 0.4 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (552 mg, 2.4 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (49) (453 mg, 63.8%). MADLI-TOF-MS: 1776.24.

[0272] Synthesis Example 14: Synthesis of Compound (53)

[0273]

[0274] Synthesis of compound 2m:

[0275] Compound 1c (747 mg, 1.0 mmol), potassium hydroxide (336.7 mg, 6.0 mmol), and DMF (10 mL) were added to a reaction flask. Nitrogen gas was purged three times. Compound L-7 (785 mg, 2.5 mmol) was added, and the mixture was heated to 90 °C and reacted for 12 h. After cooling to room temperature, the mixture was extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v = 5 / 1) as the eluent to give compound 2m (788 mg, 70.4%). MADLI-TOF-MS: 1119.16.

[0276] Synthesis of compound 3m:

[0277] Compound 2m (783 mg, 0.7 mmol) was dissolved in 1,2-dichloroethane (10 mL) under a nitrogen atmosphere, and anhydrous POCl3 (4 mL) and DMF (20 mL) were added. After reacting at room temperature for 6 hours, the reaction solution was slowly added to ice water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound 3m (532 mg, 64.6%). MADLI-TOF-MS: 1175.72.

[0278] Synthesis of compound (53):

[0279] Under a nitrogen atmosphere, compound 3m (470.3 mg, 0.4 mmol) and 5,6-difluoro-3-(dicyanomethylene)indophenone (552.4 mg, 2.4 mmol) were dissolved in chloroform (40 mL), and 4 mL of pyridine was added. The mixture was heated under reflux for 12 h. After cooling to room temperature, the mixture was poured into methanol to precipitate a solid. The solid was filtered and purified by column chromatography using petroleum ether / dichloromethane (v / v=1 / 1) as the eluent to give compound (53) (457 mg, 71.4%). MADLI-TOF-MS: 1600.53.

[0280] Organic photovoltaic (OPV) device fabrication examples

[0281] Device Example 1

[0282] Device structure such as Figure 1 As shown, the organic photovoltaic device includes a substrate, an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode layer stacked sequentially; wherein, the materials of the anode, anode buffer layer, photoactive layer, cathode buffer layer, and cathode layer are, in sequence: indium tin oxide (ITO) / 2PACz / photoactive layer material / PDINN / Ag.

[0283] Its preparation method includes the following steps:

[0284] 1) ITO substrate cleaning

[0285] Clean the ITO conductive glass with detergent, rinse it thoroughly, and then ultrasonically clean it for 15 minutes with deionized water, acetone, and isopropanol. After that, dry it with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0286] 2) Preparation of the anode buffer layer

[0287] A solution of the small molecule self-assembled material 2PACz (2PACz dissolved in ethanol at a concentration of 0.3 mg / mL) was uniformly spin-coated onto ITO in air at a speed of 3000 rpm for 30 s. After spin-coating, the material was dried at 100 °C for 10 min to obtain the anodic buffer layer.

[0288] 3) Preparation of photoactive layer

[0289] In a glove box (inert gas atmosphere), the photoactive layer material solution is uniformly spin-coated onto the anode buffer layer at a speed of 1800-3000 rpm to obtain a photoactive layer with a total thickness of approximately 100 nm.

[0290] The photoactive layer material solution is prepared by dissolving the donor and acceptor materials in chloroform and adding solid additive DIB to obtain the photoactive layer material solution. The donor material in the photoactive layer material solution is selected from polymer D18, the host acceptor material is selected from L8-BO, and the guest acceptor material is selected from compound (1). D18:L8-BO:compound (1) is added to the chloroform solution at a mass ratio of 1:1:0.2, with a total concentration of 13 mg / mL, and the amount of DIB additive is 5 mg / mL.

[0291] 4) Preparation of cathode buffer layer

[0292] The device with the photoactive layer was heat-annealed on a hot stage at 100°C for 10 min. Then, the cathode buffer layer material PDINN (prepared by dissolving PDINN in methanol to a concentration of 1.0 mg / mL) was uniformly spin-coated onto the photoactive layer at a spin speed of 3000 rpm for 30 s to obtain the cathode buffer layer.

[0293] 5) Cathode layer preparation

[0294] In high vacuum (1×10) -6 Ag is deposited onto the cathode buffer layer in millibars to form a cathode layer with a thickness of approximately 100 nm.

[0295] 6) Packaging

[0296] The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0297] Device Examples 2-13

[0298] The preparation methods of device examples 2-13 are the same as those of device example 1. The difference lies in the selection of guest acceptor materials in the photoactive layer. Specifically, the guest acceptor material compound (1) is replaced with compound (7), compound (10), compound (16), compound (17), compound (24), compound (26), compound (32), compound (33), compound (36), compound (39), compound (44) and compound (53), respectively. See Table 1 for details.

[0299] Device Comparison Example 1

[0300] The preparation method of the device in Comparative Example 1 is the same as that in Device Example 1, the difference being the selection of the guest acceptor material in the photoactive layer. Specifically, the guest acceptor material compound (1) is replaced with compound (Ref):

[0301]

[0302] The prepared organic photovoltaic device was subjected to performance testing. Under the illumination of the AM1.5 standard light simulator, the current-voltage curve of the device was tested, and the photoelectric conversion efficiency was calculated. The device data are shown in Table 1.

[0303] Table 1

[0304]

[0305] As shown in Table 1, when the ethylene glycol-containing branched organic compounds described in this invention are used as guest-acceptor materials in combination with a suitable binary system in organic photovoltaic devices, they exhibit a photoelectric conversion efficiency exceeding 20.3%, which is a significant improvement over the performance of the device in Comparative Example 1. This indicates that the branched groups containing ethylene glycol have significant advantages in regulating molecular dielectric properties and chemical energy levels, optimizing the solubility of the compound, and the molecular stacking of the active layer. As a result, the prepared device achieves better molecular dissociation and transport, effectively improving the photoelectric performance of the device.

[0306] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An organic compound containing an ethylene glycol chain, characterized in that: It has a structure as shown in general formula (I): （I） in: Y is selected from S or Se; Each time Z appears, it is independently selected from S or Se; Each time R1 appears, it is selected independently. ; Each time R3 appears, it is independently selected from a straight-chain alkyl group having 1-20 carbon atoms, either substituted or unsubstituted, or a branched alkyl group having 3-20 carbon atoms, either substituted or unsubstituted. Each time R4 appears, it is selected independently. ; Each time R5 appears, it is independently selected from straight-chain alkyl groups having 1-10 carbon atoms, branched alkyl groups having 3-10 carbon atoms, cycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms. m1 is selected from any integer from 0 to 5; m2 is selected from any integer from 1 to 5; Each time R2 appears, it is independently selected from -H, -D, substituted or unsubstituted straight-chain alkyl with 1-20 carbon atoms, substituted or unsubstituted branched alkyl with 3-20 carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 carbon atoms, substituted or unsubstituted straight-chain alkoxy with 1-20 carbon atoms, substituted or unsubstituted branched alkoxy with 3-20 carbon atoms, substituted or unsubstituted straight-chain alkathio with 1-20 carbon atoms, substituted or unsubstituted branched alkathio with 3-20 carbon atoms, substituted or unsubstituted aromatic group with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group with 5-20 cyclic atoms; Each time M appears, it is independently selected from O or C(CN)2; Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; The term "substituted or unsubstituted" indicates that the defined group is not substituted, or is substituted by one or more substituents R, wherein each substituent R is independently selected from -D, halogen, cyano, nitro, straight-chain alkyl having 1-30 carbon atoms, branched alkyl having 3-30 carbon atoms, cycloalkyl having 3-30 carbon atoms, straight-chain alkoxy having 1-30 carbon atoms, branched alkoxy having 3-30 carbon atoms, straight-chain alkylthio having 1-30 carbon atoms, branched alkylthio having 3-30 carbon atoms, aromatic group having 6-20 carbon atoms, and heteroaromatic group having 5-20 cyclic atoms, or a combination of at least two of these.

2. The organic compound containing an ethylene glycol chain according to claim 1, characterized in that: Each occurrence of R3 is independently selected from the R... a A straight-chain alkyl group, substituted or unsubstituted, having 1-16 carbon atoms; the R a Selected from , where: R 6 Each occurrence is independently selected from -D, halogen, cyano, straight-chain alkyl with 1-6 carbon atoms, or branched alkyl with 3-6 carbon atoms; m3 is selected from any integer from 0 to 5; * indicates a linking site; Preferably, each occurrence of R3 is independently selected from any of the following groups: 。 3. The organic compound containing an ethylene glycol chain according to claim 1, characterized in that: Each occurrence of R5 is independently selected from straight-chain alkyl groups having 1-6 carbon atoms, branched alkyl groups having 3-6 carbon atoms, cycloalkyl groups having 3-6 carbon atoms, and R... b Substituted or unsubstituted aromatic groups having 6-10 carbon atoms, or those modified by R b Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms; the R b Each occurrence is independently selected from -D, halogen, cyano, straight-chain alkyl with 1-6 carbon atoms, or branched alkyl with 3-6 carbon atoms; Preferably, each occurrence of R5 is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclohexyl, and methyl ethyl. b Substituted or unsubstituted phenyl, R b Substituted or unsubstituted pyridinyl groups, or those modified by R b Substituted or unsubstituted thiophene group.

4. The organic compound containing an ethylene glycol chain according to claim 1, characterized in that: Each occurrence of R1 is independently selected from any of the following groups: 。 5. The organic compound containing an ethylene glycol chain according to any one of claims 1-4, characterized in that: Each occurrence of R2 is independently selected from -H, -D, straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, cycloalkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, branched alkylthio groups having 3-20 carbon atoms, and R2. c Substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or those modified by R c Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; said R c Each occurrence is independently selected from straight-chain alkyl groups having 1-20 carbon atoms, branched alkyl groups having 3-20 carbon atoms, cycloalkyl groups having 3-20 carbon atoms, straight-chain alkoxy groups having 1-20 carbon atoms, branched alkoxy groups having 3-20 carbon atoms, straight-chain alkylthio groups having 1-20 carbon atoms, or branched alkylthio groups having 3-20 carbon atoms; Preferably, R2 is selected from -H, -D, or any of the following structures: 。 6. The organic compound containing an ethylene glycol chain according to any one of claims 1-4, characterized in that: The Selected from The Selected from ; Preferably, the , Independently selected from any of the following groups, but not limited to: 。 7. The organic compound containing an ethylene glycol chain according to claim 1, characterized in that: The organic compound containing the ethylene glycol chain is selected from any of the following structures: 。 8. A mixture comprising an organic compound containing an ethylene glycol chain as described in any one of claims 1-7.

9. A composition comprising an organic compound containing an ethylene glycol chain as described in any one of claims 1-7, or a mixture as described in claim 8, and at least one organic solvent.

10. An organic photovoltaic device comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, the photoactive layer comprising an organic compound containing an ethylene glycol chain as described in any one of claims 1-7, or a mixture as described in claim 8, or a composition as described in claim 9.

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