An organic compound and its application in organic electronic devices

Abstract

The present invention relates to an organic compound, and its structure is shown in general formula (I). The organic compound of the present invention has a simple structure and is easy to synthesize. When the organic compound is used as an active layer acceptor material in an organic electronic device, the device has a high photoelectric conversion efficiency.

Description

Technical Field

[0001] The present invention relates to the field of organic semiconductor materials, and particularly to a compound and its application in organic electronic devices, especially in organic photovoltaic devices (OPV). Background Art

[0002] As the world's largest renewable clean energy source, solar energy has the characteristic of environmental friendliness. Photovoltaic technology based on solar power generation has become an important part of human renewable energy technology. Organic solar technology has the characteristics of low cost, green and non-toxic, high efficiency, flexibility, color semi-transparency, and can be prepared by low-temperature solution method for large-area printing. It is an ideal optoelectronic conversion technology that can be applied to scenarios such as wearable electronic devices, Internet of Things, electronic price tags, building-integrated photovoltaics, and new energy vehicles, and has broad market prospects.

[0003] An organic solar cell generally consists of five parts: an anode, an anode buffer layer, an active layer, a cathode buffer layer, and a cathode. The active layer generally contains a donor material and an acceptor material. Its working principle is as follows: When sunlight passes through the transparent substrate and the electrode and enters the active layer, the donor-acceptor material absorbs photons with energy greater than its bandgap energy. Electrons are excited from the highest occupied molecular orbital (HOMO) and jump to the lowest unoccupied molecular orbital (LUMO), and corresponding holes are generated at the HOMO. Due to the relatively small relative dielectric constant of organic materials, the electrons and holes at this time exist in the form of bound excitons. Then, the excitons diffuse to the donor-acceptor interface, and under the drive of the energy level difference, the excitons dissociate to achieve charge separation. Subsequently, under the action of the built-in electric field, the free holes and electrons are respectively transported along the continuous channels of the donor and acceptor materials to reach the anode and cathode, and are collected by the electrodes and output to the external circuit to form a current. As can be seen from the above, the selection of the active layer material is crucial for the efficiency of organic solar cell devices.

[0004] In the early and middle stages of the development of organic solar cells, fullerene and its derivatives represented by PC61BM and PC71BM dominated the electron acceptor materials due to their high electron affinity, isotropic electron transport ability, and high electron mobility. This stage is usually referred to as the fullerene era. However, the limitations of the molecular structure of fullerene acceptors lead to weak absorption in the visible light region and poor energy level tunability, which limit the efficiency improvement of organic solar cells. In recent years, the emergence of non-fullerene acceptor materials has, to a certain extent, overcome the deficiencies of fullerene acceptors, greatly improving the photoelectric conversion efficiency of devices and promoting the development of the organic solar cell field. Most of the existing non-fullerene acceptor materials adopt large fused-ring cores, such as structures like ITIC and Y6. Although they exhibit excellent device performance, their structure synthesis is complex, the synthesis route is too long, the reaction yield is low, and the synthesis cost is high, which severely limits the industrial development of organic solar cells.

[0005] Therefore, it is necessary to develop new non-fullerene acceptor materials for organic solar cells with high efficiency and easy synthesis to promote the industrial development of organic solar cells. Summary of the Invention

[0006] The purpose of the present invention is to provide an organic compound with a simple structure and easy synthesis, which can be used as a small molecule acceptor material in organic solar cells to improve the photoelectric conversion efficiency of the device.

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

[0008] An organic compound has a structure shown in the general formula (I):

[0009]

[0010] Wherein:

[0011] Ar1 and Ar2 are independently selected from substituted or unsubstituted aromatic groups having 6 to 10 ring atoms, or substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms;

[0012] Y is selected from CR9R 10 or SiR9R 10 ;

[0013] R1 - R 10 are independently selected from: -H, -D, linear alkyl groups having 1 to 20 C atoms, linear alkoxy groups having 1 to 20 C atoms, linear alkylthio groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, branched or cyclic alkoxy groups having 3 to 20 C atoms, branched or cyclic alkylthio groups having 3 to 20 C atoms, silyl groups, keto groups having 1 to 20 C atoms, alkoxycarbonyl groups having 2 to 20 C atoms, aryloxycarbonyl groups having 7 to 20 C atoms, cyano groups, carbamoyl groups, halocarbonyl groups, formyl groups, isocyano groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, nitro groups, amino groups, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic groups having 6 to 10 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms, or groups formed by the combination of the above groups.

[0014] Correspondingly, the present invention also provides a mixture, including the above organic compound and at least one organic functional material, and the organic functional material is selected from anode buffer layer materials, cathode buffer layer materials, active layer donor materials, or active layer acceptor materials.

[0015] Correspondingly, the present invention further provides a composition, comprising the above-mentioned organic compound or mixture and at least one organic solvent.

[0016] Correspondingly, the present invention further provides an organic electronic device, comprising at least one functional layer, and the functional layer material comprises the above-mentioned organic compound or the above-mentioned mixture.

[0017] Compared with the prior art, the present invention has the following remarkable advantages:

[0018] (1) The organic compound according to the present invention is selected from non-fullerene acceptor materials with a non-fused ring core, and has a simple structure and is easy to synthesize. When it is used as the acceptor material of the photoactive layer of an organic solar cell in an electronic device, it exhibits excellent optoelectronic conversion performance;

[0019] (2) The organic compound according to the present invention has an asymmetric structure, has a relatively high molecular dipole moment, enhances the intermolecular charge transfer, and thus improves the charge transport ability of the material;

[0020] (3) The compound according to the present invention regulates the molecular morphology through S-O covalent bonds, improves the rigidity and planarity of the molecule; the coplanar main chain promotes the intermolecular interaction and is beneficial to the π-π stacking for charge transport. Detailed Embodiments

[0021] An organic compound, mixture, composition and their applications in organic electronic devices provided by the present application will be further described in detail below to make the purpose, technical solutions and effects of the present application clearer and more definite. 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.

[0022] As used herein, the terms "and / or", "or / and", and "and / or" include any one of two or more related listed items, and also include any and all combinations of the related listed items. The any and all combinations include combinations of any two related listed items, any more than two related listed items, or 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, this technical solution undoubtedly includes the technical solution connected by "logical AND", and also undoubtedly includes the technical solution connected by "logical OR". For example, "A and / or B" includes three parallel solutions: A, B, and A + B. Another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, includes combinations of any two or any three of A, B, C, and D, and also includes the four-item combination of A, B, C, and D (that is, the technical solution connected by "logical AND").

[0023] In the present invention, the organic photovoltaic device and the organic solar cell have the same meaning and can be interchanged.

[0024] In the present invention, the aromatic group, the aromatic, and the aromatic ring system have the same meaning and can be interchanged.

[0025] In the present invention, the heteroaromatic group, the heteroaromatic, and the heteroaromatic ring system have the same meaning and can be interchanged.

[0026] In the present invention, the "heteroatom" is a non-carbon atom and can be an N atom, an O atom, an S atom, etc.

[0027] In the present invention, "substituted" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0028] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. For example, if the general formula contains multiple Rs, then R can be independently selected from different groups.

[0029] In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or may not be substituted. When the defined group is substituted, it should be understood that the defined group may be substituted by one or more substituents R, and the R is selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1-20 C atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR’R”, silyl group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, halocarbonyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may also be further substituted by substituents acceptable in the art; it is understandable that in -NR’R”, R’ and R” are each independently selected from, but not limited to: H, deuterium atom (-D), cyano group, isocyano group, nitro group or halogen, alkyl group containing 1-10 C atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1-10 C atoms, heterocyclic group containing 3-10 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, silyl group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, halocarbonyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may also be further substituted by substituents acceptable in the art.

[0030] In the present invention, "number of ring atoms" means the number of atoms among the atoms constituting the ring itself in a structural compound obtained by bonding atoms in a ring (for example, monocyclic compound, fused-ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound). 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 "number of ring atoms" described below under the condition of no special explanation. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thiophenyl group is 5.

[0031] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, which can be a monocyclic aryl group, a fused-ring aryl group, or a polycyclic aryl group. For polycyclic ring systems, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" refers to an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, dibenzofuranyl, acenaphthylenyl and their derivatives. It can be understood that multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N or O atoms), specifically such as acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aryl groups.

[0032] "Heteroaryl or heteroaromatic group" refers to a group in which at least one carbon atom in the aryl group is replaced by a non-carbon atom, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms" refers to a heteroaryl group having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted heteroaryl group having 6 to 14 ring atoms, and the heteroaryl group is optionally further substituted. Suitable examples include but are not limited to: thienyl, furyl, pyrrolyl, dioxolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuryl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furanopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, perimidinyl, quinazolinone, dibenzothienyl, dibenzofuranyl, carbazolyl and their derivatives.

[0033] In the present invention, "alkyl" may represent straight-chain, branched-chain, and / or cyclic alkyl. The number of carbon atoms in the alkyl may be 1 to 50, 1 to 30, 1 to 20, 1 to 15, or 1 to 6. Phrases containing this term, for example, "C1-9 alkyl", refer to an alkyl containing 1 to 9 carbon atoms, and each occurrence may independently be a C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyl octyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc.

[0034] "Amino" refers to a derivative of an amine and has a structural feature of the formula -N(X)2, where each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic group, etc. Non-limiting types of amino include -NH2, -N(alkyl)2, -NH(alkyl), -N(cycloalkyl)2, -NH(cycloalkyl), -N(heterocyclic group)2, -NH(heterocyclic group), -N(aryl)2, -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclic group), -N(cycloalkyl)(heterocyclic group), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0035] In the present invention, unless otherwise defined, hydroxyl group refers to -OH, carboxyl group refers to -COOH, carbonyl group refers to -C(=O)-, amino group refers to -NH2, formyl group refers to -C(=O)H, halocarbonyl group refers to -C(=O)Z (wherein Z represents a halogen), carbamoyl group refers to -C(=O)NH2, isocyanate group refers to -NCO, and isothiocyanate group refers to -NCS.

[0036] The term "alkoxy group" refers to a group having the structure "-O-alkyl", that is, the alkyl group defined above is connected to other groups via an oxygen atom. For phrases containing this term, suitable examples include, but are not limited to: methoxy group (-O-CH3 or -OMe), ethoxy group (-O-CH2CH3 or -OEt), and tert-butoxy group (-O-C(CH3)3 or -OtBu).

[0037] The term "alkylthio group" refers to a group having the structure "-S-alkyl", that is, the alkyl group defined above is connected to other groups via a sulfur atom. For phrases containing this term, suitable examples include, but are not limited to: methylthio group (-S-CH3 or -SMe), ethylthio group (-S-CH2CH3 or -SEt), and tert-butylthio group (-S-C(CH3)3 or -StBu).

[0038] In the present invention, "*" connected to a single bond represents a connection or fusion site;

[0039] In the present invention, when the connection site is not specified in a group, it means that any optional connection site in the group can be used as the connection site;

[0040] In the present invention, when a group contains multiple substituents with the same symbol, each substituent can be the same or different from each other. For example The 6 Rs on the benzene ring can be the same or different from each other.

[0041] In the present invention, "its combination", "any combination thereof", "any combination mode thereof", "combination", etc. include all suitable combination modes of any two, any three, or any three or more groups listed.

[0042] In the present invention, "further", "even further", "especially", etc. are used for descriptive purposes, indicating differences in content, but should not be construed as limiting the protection scope of the present invention.

[0043] In the present invention, "optionally", "optional", "option", mean that it can be present or absent, that is, it refers to any one of the two alternative schemes of "present" or "absent". If "optional" appears multiple times in a technical solution, unless otherwise specified and there are no contradictions or mutual restrictions, each "optional" is independent of each other.

[0044] In the present invention, among the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, and also includes an open-ended technical solution containing the listed features.

[0045] The present invention relates to an organic compound having a structure shown in the general formula (I):

[0046]

[0047] Wherein:

[0048] Ar1 and Ar2 are independently selected from a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms;

[0049] Y is selected from CR9R 10 or SiR9R 10 ;

[0050] R1 - R 10 are each independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic alkylthio group having 3 to 20 C atoms, a silyl group, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a halocarbonyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amino group, -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or a group formed by combining the above groups;

[0051] In one embodiment, R1 - R 10 are each independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic alkylthio group having 3 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, a cyano group, a nitro group, -Cl, -Br, -F, -I, a phenyl group, a heteroaromatic group having 5 - 6 ring atoms, or a group formed by combining the above groups.

[0052] In one embodiment, R1 is selected from a straight-chain alkoxy group having 1 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms; wherein R1 is unsubstituted or substituted with one or more deuteriums. Further, R2 is selected from a straight-chain alkoxy group having 1 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms, wherein R2 is unsubstituted or substituted with one or more deuteriums; or R3 is selected from a straight-chain alkoxy group having 1 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms, wherein R3 is unsubstituted or substituted with one or more deuteriums.

[0053] In one embodiment, the general formula (I) is selected from the structures represented by the general formula (II-1) or (II-2):

[0054]

[0055]

[0056] Wherein:

[0057] R 11 -R 12 is selected from: a straight-chain alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms; R 11 -R 12 is unsubstituted or substituted with one or more deuteriums.

[0058] In one embodiment, in the general formula (II-1) and the general formula (II-2), R 11 and R 12 are selected from the same group; preferably, R 11 and R 12 are selected from methyl, ethyl, straight-chain or branched C3H7, straight-chain or branched C4H9, straight-chain or branched C5H 11 、straight-chain or branched C6H 13 、straight-chain or branched C7H 15 、straight-chain or branched C8H 17 、straight-chain or branched C9H 19 、straight-chain or branched C 10 H 21 、straight-chain or branched C 11 H 23 、straight-chain or branched C 12 H 25 、straight-chain or branched C 13 H 27 、straight-chain or branched C 14 H 29 、straight-chain or branched C 15 H 31 、straight-chain or branched C 16 H 33; One or more H atoms in the above groups are unsubstituted or substituted with deuterium.

[0059] In one embodiment, R2, R3, and R4 are selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic alkylthio group having 3 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, a cyano group, a nitro group, -Cl, -Br, -F, -I, a phenyl group, a heteroaromatic group having 5 - 6 ring atoms, or a group formed by combining the above groups.

[0060] In one embodiment, R2 in the general formula (II-1) is selected from: -H, -D, a straight-chain alkyl group having 1 to 15 C atoms, a straight-chain alkoxy group having 1 to 15 C atoms, a straight-chain alkylthio group having 1 to 15 C atoms, a branched or cyclic alkyl group having 3 to 15 C atoms, a branched or cyclic alkoxy group having 3 to 15 C atoms, a branched or cyclic alkylthio group having 3 to 15 C atoms, an alkoxycarbonyl group having 2 to 15 C atoms, a cyano group, a nitro group, -Cl, -Br, -F, -I, a phenyl group, a heteroaromatic group having 5 - 6 ring atoms, or a group formed by combining the above groups.

[0061] In one embodiment, R3 in the general formula (II-2) is selected from: -H, -D, a straight-chain alkyl group having 1 to 15 C atoms, a straight-chain alkoxy group having 1 to 15 C atoms, a straight-chain alkylthio group having 1 to 15 C atoms, a branched or cyclic alkyl group having 3 to 15 C atoms, a branched or cyclic alkoxy group having 3 to 15 C atoms, a branched or cyclic alkylthio group having 3 to 15 C atoms, an alkoxycarbonyl group having 2 to 15 C atoms, a cyano group, a nitro group, -Cl, -Br, -F, -I, a phenyl group, a heteroaromatic group having 5 - 6 ring atoms, or a group formed by combining the above groups.

[0062] In one embodiment, R4 is selected from: -H, -D, a straight-chain alkyl group having 1 to 15 C atoms, a straight-chain alkoxy group having 1 to 15 C atoms, a straight-chain alkylthio group having 1 to 15 C atoms, a branched or cyclic alkyl group having 3 to 15 C atoms, a branched or cyclic alkoxy group having 3 to 15 C atoms, a branched or cyclic alkylthio group having 3 to 15 C atoms, an alkoxycarbonyl group having 2 to 15 C atoms, a cyano group, a nitro group, -Cl, -Br, -F, -I, a phenyl group, a heteroaromatic group having 5 - 6 ring atoms, or a group formed by combining the above groups.

[0063] In one embodiment, R5, R6, R7, and R8 are selected from: -H, -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a branched or cyclic alkylthio group having 3 to 20 carbon atoms, or a group formed by combining the above groups.

[0064] In one embodiment, R5-R6 are selected from: -H, -D, a straight-chain alkyl group having 1 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms, or a group formed by combining the above groups. Further, R5-R6 are selected from: -H, -D, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched alkyl group having 3 to 10 carbon atoms, or a group formed by combining the above groups.

[0065] In one embodiment, R6 is selected from a straight-chain alkyl group having 1 to 12 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms, and one or more H atoms in the above groups are unsubstituted or replaced by deuterium. In one embodiment, R6 is selected from a straight-chain alkyl group having 4 to 12 carbon atoms, or a branched alkyl group having 4 to 12 carbon atoms, and one or more H atoms in the above groups are unsubstituted or replaced by deuterium.

[0066] In one embodiment, R7-R8 are selected from: -H, -D, a straight-chain alkyl group having 1 to 15 carbon atoms, a straight-chain alkoxy group having 1 to 15 carbon atoms, a straight-chain alkylthio group having 1 to 15 carbon atoms, a branched or cyclic alkyl group having 3 to 15 carbon atoms, a branched or cyclic alkoxy group having 3 to 15 carbon atoms, a branched or cyclic alkylthio group having 3 to 15 carbon atoms, or a group formed by combining the above groups.

[0067] In one embodiment, R7-R8 are selected from: -H, -D, a straight-chain alkyl group having 1 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms, or a group formed by combining the above groups.

[0068] In one embodiment, R8 is selected from a straight-chain alkyl group having 1 to 12 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms, and one or more H atoms in the above groups are unsubstituted or replaced by deuterium. In one embodiment, R8 is selected from a straight-chain alkyl group having 4 to 12 carbon atoms, or a branched alkyl group having 4 to 12 carbon atoms, and one or more H atoms in the above groups are unsubstituted or replaced by deuterium.

[0069] In one embodiment, R9-R 10 is selected from: -H, -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, phenyl, or a group formed by combining the above groups.

[0070] In one embodiment, R9-R 10 is selected from: -H, -D, a straight-chain alkyl group having 1 to 15 C atoms, a branched-chain alkyl group having 3 to 15 C atoms, phenyl, or a group formed by combining the above groups.

[0071] In one embodiment, Ar1 and Ar2 are independently selected from any one of the structures (A-1)-(A-5):

[0072]

[0073] wherein: X is independently selected from CR 13 or N;

[0074] Each occurrence of W is independently selected from O, S or Se;

[0075] R 13 Each occurrence is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain alkylthio group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic alkylthio group having 3 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, cyano, nitro, -Cl, -Br, -F, -I, phenyl, a heteroaromatic group having 5-6 ring atoms, or a group formed by combining the above groups.

[0076] It should be noted that when X is a connection site, X is selected from C atoms.

[0077] In one embodiment, Ar1 and Ar2 are independently selected from any one of the structures (B-1)-(B-10):

[0078]

[0079] wherein: * represents a connection site.

[0080] In one embodiment, is selected from the following groups:

[0081]

[0082] wherein: * represents a connection site.

[0083] In one embodiment, R 13 Each occurrence is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 6 C atoms, a branched-chain alkyl group having 3 to 6 C atoms, cyano, nitro, -Cl, -Br, -F, -I, or a group formed by combining the above groups.

[0084] In one embodiment, W is selected from S.

[0085] In one embodiment, the organic compound according to the present invention is selected from the following structures but not limited thereto:

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092] Wherein: The above compounds may be further substituted.

[0093] The organic compound according to the present invention can be used as an active layer material in organic electronic devices; preferably, the organic compound according to the present invention can be used as an active layer acceptor material in organic solar devices.

[0094] The present invention further relates to a mixture comprising the organic compound as described above and at least one other organic functional material, and the at least one other organic functional material can be selected from an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material. The weight ratio thereof to the other organic functional material is from 1:99 to 99:1. In one embodiment, the photoactive layer comprises a donor material and an acceptor material, and the weight ratio is donor material / acceptor material = 1 / 1.2.

[0095] In one embodiment, the other organic functional material is selected from an active layer donor material or an active layer acceptor material. Preferably, the other organic functional material is selected from an active layer donor material.

[0096] This application further relates to an electron acceptor material, and the electron acceptor material is selected from the organic compound or mixture as described above; when the electron acceptor material is selected from the mixture as described above, the other functional material is selected from an active layer acceptor material; preferably, the other functional material is selected from fullerenes and their derivatives.

[0097] This application also relates to a composition comprising at least one of the organic compound or mixture as described above and at least one organic solvent.

[0098] The organic solvent is selected from at least one of aromatic or heteroaromatic-based solvents, ester-based solvents, aromatic ketone-based solvents, aromatic ether-based solvents, aliphatic ketones, aliphatic ethers, alicyclic compounds, olefinic compounds, borate compounds, and phosphate compounds.

[0099] In at least one embodiment, in the composition, the organic solvent is selected from aromatic or heteroaromatic-based solvents.

[0100] The aromatic or heteroaromatic-based solvent may be selected from, but not limited to, chlorobenzene, toluene, o-xylene, diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, tripentylbenzene, amyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furoate, and ethyl 2-furoate.

[0101] The ester-based solvent may be selected from, but not limited to, alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkanolactones, alkyl oleates, etc. At least one of octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate is particularly preferred.

[0102] The aromatic ketone-based solvent may be selected from, but not limited to, 1-tetralone, 2-tetralone, 2-(phenyloxiranyl)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives. Among them, as examples, the derivatives may be selected from, but not limited to, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, and 2-methylpropiophenone.

[0103] The aromatic ether-based solvent can be selected from, but not limited to, at least one of 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenzyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, and ethyl-2-naphthyl ether.

[0104] The aliphatic ketone-based solvent can be selected from, but not limited to, at least one of 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-pentyl ketone, etc.; or aliphatic ethers, such as, at least one of pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

[0105] In one embodiment, the organic solvent is selected from chlorobenzene, toluene, o-xylene, or chloroform.

[0106] It can be understood that the organic solvent can be used alone or as a mixed solvent of two or more organic solvents.

[0107] In one embodiment, the composition of the present application includes at least one of the above-described organic compounds or mixtures, and at least one organic solvent, and may further include another organic solvent.

[0108] The another organic solvent can be selected from, but not limited to, at least one of methanol, ethanol, 2-methoxyethanol, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide (DMSO), tetralin, decalin, and indene.

[0109] In one embodiment, the organic solvent suitable for the present application is a solvent with Hansen solubility parameters in the following range:

[0110] δd (dispersion force) is at 17.0 MPa1 / 2 -23.2 MPa 1 / 2 Within the range, especially at 18.5 MPa 1 / 2 -21.0 MPa 1 / 2 range;

[0111] δp (polar force) is within 0.2 MPa 1 / 2 -12.5 MPa 1 / 2 range, especially at 2.0 MPa 1 / 2 -6.0 MPa 1 / 2 range;

[0112] δh (hydrogen bond force) is within 0.9 MPa 1 / 2 -14.2 MPa 1 / 2 range, especially at 2.0 MPa 1 / 2 -6.0 MPa 1 / 2 range.

[0113] In one embodiment, for the composition according to the present application, the boiling point of the organic solvent needs to be considered when selecting. In at least some embodiments, the boiling point of the organic solvent is ≥150 °C; preferably ≥180 °C; more preferably ≥200 °C; still more preferably ≥250 °C; most preferably ≥300 °C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printing head.

[0114] It can be understood that the organic solvent can evaporate from the solvent system to form a thin film including the organic compound.

[0115] In one embodiment, the composition is a solution. In still some other embodiments, the composition is a suspension. The solution or suspension may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives may be selected from but not limited to at least one of surface active compounds, lubricants, wetting agents, dispersants, water repellents, and adhesives.

[0116] The composition may also be referred to as ink.

[0117] When used in a printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of a suitable ink are suitable for a specific substrate and a specific printing method.

[0118] In one embodiment, the surface tension of the ink according to the present application at the working temperature or at 25 °C is in the range of about 19 dyne / cm to 50 dyne / cm; more preferably 22 dyne / cm to 35 dyne / cm; most preferably 25 dyne / cm to 33 dyne / cm.

[0119] In one embodiment, the viscosity of the ink according to the present application ranges from 1 cps to 100 cps at the working temperature or 25 °C; preferably from 1 cps to 50 cps; more preferably from 1.5 cps to 20 cps; most preferably from 4.0 cps to 20 cps.

[0120] It can be understood that the ink having the above surface tension and viscosity will facilitate inkjet printing.

[0121] It can be understood that the viscosity of the ink can be adjusted by different methods, such as by selecting a suitable solvent and the concentration of functional materials in the ink. The ink containing organic compounds according to the present application can conveniently adjust the printing ink within an appropriate range according to the printing method used. Among the compositions of the present application, the mass percentage of the organic compound or mixture is 0.01 wt% to 15 wt%, preferably 0.1 wt% to 10 wt%, more preferably 0.2 wt% to 5 wt%, and most preferably 0.25 wt% to 3 wt%.

[0122] The present application also relates to the use of the above composition as a coating or printing ink in the preparation of organic electronic devices. In one embodiment, the composition is used to prepare organic electronic devices by a preparation method of printing or coating. The preparation method of printing or coating can be, but is not limited to, inkjet printing, gravure printing, spraying, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, reverse roller printing, lithography, flexography, rotary printing, spraying, brush coating, pad printing, slot coating, etc. Preferred are slot coating, spin coating and inkjet printing.

[0123] The present application further relates to the application of an organic compound or mixture or composition as described above in an organic electronic device. The organic electronic device can be selected from, but is not limited to, organic solar cells (OPV), organic photodetectors (OPD), organic light-emitting diodes (OLED), organic light-emitting electrochemical cells (OLEEC), organic field-effect transistors (OFET), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, and organic plasmon-emitting diodes, etc., and is particularly preferably OPV.

[0124] The present application also relates to an organic electronic device, including at least one functional layer, and the functional layer contains the above organic compound or the above mixture or is prepared from the above composition. Preferably, the functional layer is selected from an anode buffer layer, an active layer or a cathode buffer layer.

[0125] In one embodiment, the organic electronic device at least includes a first electrode, a second electrode, and one or more functional layers located between the first electrode and the second electrode. Preferably, the one or more functional layers are selected from active layers; more preferably, the one or more functional layers are selected from an anode buffer layer, an active layer, and a cathode buffer layer.

[0126] It should be noted that in order to improve the performance of the organic solar cell device, the functional layer may further include other functional layers, including but not limited to a charge injection layer and / or a charge blocking layer.

[0127] Furthermore, the organic solar cell further includes a substrate. Specifically, the substrate can be disposed below the first electrode and on a side away from the functional layer.

[0128] In one embodiment, the first electrode is an anode and the second electrode is a cathode; in another embodiment, the first electrode can be a cathode and the second electrode can be an anode.

[0129] In one embodiment, as the substrate, a substrate having excellent transparency, surface smoothness, ease of operation, and waterproofness can be used. Specifically, a glass substrate, a thin film glass substrate, or a transparent plastic substrate can be used. The plastic substrate can include films in the form of a single layer or multiple layers, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), and polyimide (PI), etc., but not limited thereto, and substrates commonly used for organic solar cells can also be used.

[0130] At least one of the anode electrode and the cathode electrode is made of a transparent or semi-transparent material. The electrode material can include metals, such as silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd), magnesium (Mg), vanadium (V), chromium (Cr), zinc (Zn), or their alloys, etc.; materials having a multilayer structure, such as Al / Li, Al / BaF2, and Al / BaF2 / Ba, Al / Yb, etc.; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO∶Al or SnO2∶Sb; and conductive polymers, such as PEDOT:PSS (poly(3,4-ethylenedioxythiophene)) of poly(styrenesulfonic acid), polypyrrole, and polyaniline, etc., but not limited thereto.

[0131] The active layer contains an electron donor material and an electron acceptor material. In this specification, the active layer material can mean an electron donor material and an electron acceptor material.

[0132] Specifically, the electron donor material can be various polymer materials or small molecule materials. The polymer materials 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 bandgap polymer material systems, such as those copolymerized from benzothiadiazoles (BT, BBT), quinoxalines (QU, PQ), pyrazines (TP, PQ) and electron-rich groups (such as thiophene derivatives), such as PCDTBT, PCPDTBT, PFO-DBT, PTB7, PM6, J52, PTQ10, etc. The small molecule materials can be selected from one or more of the following: copper(II) phthalocyanine, zinc phthalocyanine, tris[4-(5-dicyanomethylene methyl-2-thienyl)phenyl]amine, 2,4-bis[4-(N,N-dibenzylamino)-2,6-dihydroxyphenyl] squarylium, benz[a]anthracene and pentacene, B8, B10, etc.

[0133] The photoactive layer can be formed by the following method: dissolving a photoactive material, such as an electron donor and / or an electron acceptor, in an organic solvent, and then coating the resulting solution by methods such as spin coating, dip coating, screen printing, gravure printing, spraying, doctor blading, slot die coating, and inkjet printing, but not limited thereto.

[0134] The anode buffer layer material can be selected from PEDOT:PSS (poly(3,4-ethylenedioxythiophene)) of poly(styrenesulfonic acid), molybdenum oxide (MoOx), vanadium pentoxide (V2O5), nickel oxide (NiO), tungsten oxide (WOx, preferably, x is selected from 2 or 3), etc., but not limited thereto.

[0135] The cathode buffer layer material can be an electron-withdrawing metal oxide or polymer. The metal oxide can be a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc. The polymer can be PFN-Br or PFN, etc., but not limited thereto.

[0136] The present invention also relates to the application of the organic solar cell according to the present invention in various devices, including, but not limited to, automotive and building integrated photovoltaics (BIPV), electronic price tags, indoor photovoltaics, Internet of Things, smart agriculture, and so on.

[0137] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims define the scope of the present invention. Under the guidance of the inventive concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0138] Examples of the organic compounds and organic electronic devices of the present invention are given here, but the present invention is not limited to the following embodiments.

[0139] Example 1: Synthesis of Compound 1

[0140]

[0141] Synthesis of Compounds 1-3:

[0142] Accurately weigh Compound 1-1 (24.6 g, 50 mmol), Compound 1-2 (34.6 g, 50 mmol), and 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (1.83 g, 2.5 mmol), and add them to a 1000 ml three-necked flask in sequence. Then add 400 ml of anhydrous toluene. After purging with argon three times, heat the mixture to 80 °C and react for 12 h. Cool to room temperature and remove the excess solvent by distillation under reduced pressure. Dissolve the crude product in dichloromethane, add silica gel for sample mixing, and perform column chromatography. The eluent is PE:DCM = 8:1 (volume ratio) to obtain about 29.3 g of Compound 1-3, with a yield of 72%.

[0143] Synthesis of Compound 1-5:

[0144] Accurately weigh Compound 1-3 (24.4 g, 30 mmol), Compound 1-4 (12.9 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and add them to a 1000 ml three-necked flask in sequence. Then add 450 ml of anhydrous toluene. After purging with argon three times, heat the mixture to 110 °C and react for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Perform column chromatography with silica gel for sample mixing. The eluent is PE:EA = 10:1 (volume ratio) to obtain about 17.8 g of Compound 1-5, with a yield of 68%.

[0145] Synthesis of Compound 1-6:

[0146] Accurately weigh Compound 1-5 (13.1 g, 15 mmol) and add it to a 500 ml three-necked flask. Add 200 ml of anhydrous DMF. After purging with argon three times, cool the reaction system to 0 °C in an ice-salt bath. Weigh phosphorus oxychloride (14.7 g, 96 mmol) and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h and then heat to 80 °C and react for 12 h. Cool to room temperature, pour the reaction solution into water for quenching, extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Add silica gel for sample mixing and perform column chromatography. The eluent is PE:DCM = 6:1 (volume ratio) to obtain about 11.3 g of Compound 1-6, with a yield of 81%.

[0147] Synthesis of Compound 1:

[0148] Accurately weigh Compound 1-6 (9.3 g, 10 mmol), Compound 1-7 (5.1 g, 22 mmol), and 2.5 ml of pyridine, and sequentially add them to a 500 ml three-necked flask. Add 200 ml of chloroform, replace argon three times, and then heat to 60 °C and react for 12 h. Cool to room temperature and remove the excess solvent by vacuum distillation. The crude product is washed with 100 ml of methanol, filtered, and the filter cake is dissolved in dichloromethane and added with silica gel for column chromatography. The eluent is PE:DCM = 5:1 (volume ratio), and about 10.4 g of Compound 1 is obtained, with a yield of 77%. MS: 1353.65.

[0149] Example 2: Synthesis of Compound 6

[0150]

[0151] Synthesis of Compound 6-2

[0152] Accurately weigh Compound 1-3 (24.4 g, 30 mmol), Compound 6-1 (16.2 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and sequentially add them to a 1000 ml three-necked flask. Add 450 ml of anhydrous toluene, replace argon three times, and then heat to 110 °C and react for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by vacuum distillation. Column chromatography with silica gel loading, and the eluent is PE:EA = 9:1 (volume ratio), and about 21.6 g of Compound 6-2 is obtained, with a yield of 73%.

[0153] Synthesis of Compound 6-3

[0154] Accurately weigh Compound 6-2 (14.8 g, 15 mmol), add it to a 500 ml three-necked flask, add 200 ml of anhydrous DMF, replace argon three times, and then cool to 0 °C in an ice-salt bath. Weigh phosphorus oxychloride (14.7 g, 96 mmol) and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat to 80 °C and react for 12 h. Cool to room temperature, quench the reaction solution by pouring it into water, extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by vacuum distillation. Add silica gel for column chromatography, and the eluent is PE:DCM = 9:1 (volume ratio), and about 12.2 g of Compound 6-3 is obtained, with a yield of 78%.

[0155] Synthesis of Compound 6

[0156] Accurately weigh Compound 6-3 (10.4 g, 10 mmol), Compound 6-4 (5.8 g, 22 mmol), and 2.5 ml of pyridine, and add them successively to a 500-ml three-necked flask. Then add 200 ml of chloroform. After displacing argon three times, heat the mixture to 60 °C and react for 12 h. Cool to room temperature and remove the excess solvent by distillation under reduced pressure. Wash the crude product with 100 ml of methanol, filter it, dissolve the filter cake in dichloromethane, mix it with silica gel, and perform column chromatography. The eluent is PE:DCM = 6:1 (volume ratio) to obtain about 10.5 g of Compound 6, with a yield of 69%. MS: 1531.93.

[0157] Example 3: Synthesis of Compound 19

[0158]

[0159] Synthesis of Compound 19-2

[0160] Accurately weigh Compound 1-1 (24.6 g, 50 mmol), Compound 19-1 (40.2 g, 50 mmol), and 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (1.83 g, 2.5 mmol), and add them successively to a 1000-ml three-necked flask. Then add 400 ml of anhydrous toluene. After displacing argon three times, heat the mixture to 80 °C and react for 12 h. Cool to room temperature and remove the excess solvent by distillation under reduced pressure. Dissolve the crude product in dichloromethane, mix it with silica gel, and perform column chromatography. The eluent is PE:DCM = 5:1 (volume ratio) to obtain about 37.5 g of Compound 19-2, with a yield of 81%.

[0161] Synthesis of Compound 19-3

[0162] Accurately weigh Compound 19-2 (27.8 g, 30 mmol), Compound 6-1 (16.2 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and add them successively to a 1000-ml three-necked flask. Then add 450 ml of anhydrous toluene. After displacing argon three times, heat the mixture to 110 °C and react for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract it three times with ethyl acetate, combine the organic phases, dry them with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Perform column chromatography with silica gel mixing. The eluent is PE:EA = 8:1 (volume ratio) to obtain about 23.7 g of Compound 19-3, with a yield of 72%.

[0163] Synthesis of Compound 19-4

[0164] Accurately weigh compound 19-3 (16.5 g, 15 mmol), add it to a 500 ml three-necked flask, add 200 ml of anhydrous DMF. After replacing argon three times, cool it to 0 °C in an ice-salt bath. Weigh phosphorus oxychloride (14.7 g, 96 mmol) and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then raise the temperature to 80 °C and react for 12 h. Cool to room temperature, pour the reaction solution into water to quench it, extract it three times with dichloromethane, combine the organic phases, dry them with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Add silica gel for sample mixing and column chromatography, and the eluent is PE:DCM = 7:1 (volume ratio) to obtain about 13.0 g of compound 19-4, yield: 75%.

[0165] Synthesis of Compound 19

[0166] Accurately weigh compound 19-4 (11.5 g, 10 mmol), compound 1-7 (5.1 g, 22 mmol), and 2.5 ml of pyridine, and add them successively to a 500 ml three-necked flask. Add 200 ml of chloroform, replace argon three times, and then raise the temperature to 60 °C and react for 12 h. Cool to room temperature and remove the excess solvent by distillation under reduced pressure. Wash the crude product with 100 ml of methanol, filter it, dissolve the filter cake with dichloromethane, add silica gel for sample mixing and column chromatography, and the eluent is PE:DCM = 4:1 (volume ratio) to obtain about 10.7 g of compound 19, yield: 68%. MS: 1578.55.

[0167] Example 4: Synthesis of Compound 37

[0168]

[0169] Synthesis of Compound 37-2:

[0170] Accurately weigh compound 37-1 (30.2 g, 50 mmol), compound 1-2 (34.6 g, 50 mmol), and 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (1.83 g, 2.5 mmol), and add them successively to a 1000 ml three-necked flask. Add 400 ml of anhydrous toluene, replace argon three times, and then raise the temperature to 80 °C and react for 12 h. Cool to room temperature and remove the excess solvent by distillation under reduced pressure. Dissolve the crude product with dichloromethane, add silica gel for sample mixing and column chromatography, and the eluent is PE:DCM = 7:1 (volume ratio) to obtain about 39.4 g of compound 37-2, yield: 85%.

[0171] Synthesis of Compound 37-4

[0172] Accurately weigh Compound 37-2 (27.8 g, 30 mmol), Compound 37-3 (15.4 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and sequentially add them to a 1000 ml three-necked flask. Add 450 ml of anhydrous toluene, replace argon three times, and then heat to 110 °C and react for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by rotary evaporation under reduced pressure. Column chromatography with silica gel as the stationary phase, and the eluent is PE:EA = 9:1 (volume ratio) to obtain approximately 24.7 g of Compound 37-4, yield: 77%.

[0173] Synthesis of Compound 37-5

[0174] Accurately weigh Compound 37-4 (16.0 g, 15 mmol), add it to a 500 ml three-necked flask, add 200 ml of anhydrous DMF, replace argon three times, then cool to 0 °C in an ice-salt bath, weigh phosphorus oxychloride (14.7 g, 96 mmol), and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat to 80 °C and react for 12 h. Cool to room temperature, quench the reaction solution by pouring it into water, extract three times with dichloromethane, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by rotary evaporation under reduced pressure. Add silica gel for sample mixing and column chromatography, and the eluent is PE:DCM = 7:1 (volume ratio) to obtain approximately 11.7 g of Compound 37-5, yield: 69%.

[0175] Synthesis of Compound 37

[0176] Accurately weigh Compound 37-5 (11.3 g, 10 mmol), Compound 37-6 (6.1 g, 22 mmol), and 2.5 ml of pyridine, and sequentially add them to a 500 ml three-necked flask. Add 200 ml of chloroform, replace argon three times, and then heat to 60 °C and react for 12 h. Cool to room temperature, and remove the excess solvent by rotary evaporation under reduced pressure. Wash the crude product with 100 ml of methanol, filter, dissolve the filter cake with dichloromethane, add silica gel for sample mixing and column chromatography, and the eluent is PE:DCM = 8:1 (volume ratio) to obtain approximately 10.9 g of Compound 37, yield: 66%. MS: 1648.73

[0177] Example 5: Synthesis of Compound 46

[0178]

[0179] Synthesis of Compound 46-1

[0180] Accurately weigh Compound 37-2 (27.8 g, 30 mmol), Compound 6-1 (16.2 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and sequentially add them to a 1000 ml three-necked flask. Add 450 ml of anhydrous toluene, replace argon three times, and then heat to 110 °C and react for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Column chromatography with silica gel as the stationary phase, and the eluent is PE:EA = 5:1 (volume ratio) to obtain approximately 24.4 g of Compound 46-1, yield: 74%.

[0181] Synthesis of Compound 46-2

[0182] Accurately weigh Compound 46-1 (16.5 g, 15 mmol), add it to a 500 ml three-necked flask, add 200 ml of anhydrous DMF, replace argon three times, then cool to 0 °C in an ice-salt bath, weigh phosphorus oxychloride (14.7 g, 96 mmol) and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat to 80 °C and react for 12 h. Cool to room temperature, pour the reaction solution into water to quench the reaction, extract three times with dichloromethane, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Add silica gel for column chromatography, and the eluent is PE:DCM = 6:1 (volume ratio) to obtain approximately 13.2 g of Compound 46-2, yield: 76%.

[0183] Synthesis of Compound 46

[0184] Accurately weigh Compound 46-2 (11.5 g, 10 mmol), Compound 46-3 (6.2 g, 22 mmol), and 2.5 ml of pyridine, and sequentially add them to a 500 ml three-necked flask. Add 200 ml of chloroform, replace argon three times, and then heat to 60 °C and react for 12 h. Cool to room temperature, and remove the excess solvent by distillation under reduced pressure. Wash the crude product with 100 ml of methanol, filter, dissolve the filter cake in dichloromethane, add silica gel for column chromatography, and the eluent is PE:DCM = 6:1 (volume ratio) to obtain approximately 12.3 g of Compound 46, yield: 73%. MS: 1677.69.

[0185] Example 6: Synthesis of Compound 67

[0186]

[0187] Synthesis of Compound 67-2:

[0188] Accurately weigh Compound 67-1 (35.8 g, 50 mmol), Compound 1-2 (34.6 g, 50 mmol), and dichlorobis(η5-cyclopentadienyl)bis(diphenylphosphine) palladium(II) (1.83 g, 2.5 mmol), and successively add them into a 1000 ml three-necked flask. Add 400 ml of anhydrous toluene, displace argon three times, and then heat to 80 °C for reaction for 12 h. Cool to room temperature, and distill off the excess solvent under reduced pressure. Dissolve the crude product in dichloromethane, add silica gel for sample mixing, and perform column chromatography. The eluent is PE:DCM = 6:1 (volume ratio) to obtain approximately 40 g of Compound 67-2, yield: 77%.

[0189] Synthesis of Compound 67-3

[0190] Accurately weigh Compound 67-2 (31.2 g, 30 mmol), Compound 1-4 (12.9 g, 30 mmol), and palladium(0) tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and successively add them into a 1000 ml three-necked flask. Add 450 ml of anhydrous toluene, displace argon three times, and then heat to 110 °C for reaction for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, and distill off the excess solvent under reduced pressure. Perform column chromatography with silica gel for sample mixing. The eluent is PE:EA = 6:1 (volume ratio) to obtain approximately 24.7 g of Compound 67-3, yield: 85%.

[0191] Synthesis of Compound 67-4

[0192] Accurately weigh Compound 67-3 (16.5 g, 15 mmol), add it into a 500 ml three-necked flask, add 200 ml of anhydrous DMF, displace argon three times, cool to 0 °C in an ice-salt bath, weigh phosphorus oxychloride (14.7 g, 96 mmol), and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat to 80 °C for reaction for 12 h. Cool to room temperature, pour the reaction solution into water for quenching, extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and distill off the excess solvent under reduced pressure. Add silica gel for sample mixing and perform column chromatography. The eluent is PE:DCM = 9:1 (volume ratio) to obtain approximately 12.8 g of Compound 67-4, yield: 74%.

[0193] Synthesis of Compound 67

[0194] Accurately weigh Compound 67-4 (11.5 g, 10 mmol), Compound 1-7 (5.1 g, 22 mmol), and 2.5 ml of pyridine, and sequentially add them into a 500-ml three-necked flask. Then add 200 ml of chloroform. After displacing argon three times, heat the mixture to 60 °C and react for 12 h. Cool to room temperature and distill off the excess solvent under reduced pressure. Wash the crude product with 100 ml of methanol, filter, dissolve the filter cake in dichloromethane, mix it with silica gel for column chromatography, and use PE:DCM = 9:1 (volume ratio) as the eluent to obtain about 10.9 g of Compound 67, with a yield of 69%. MS: 1578.81.

[0195] Example 7: Synthesis of Compound 69

[0196]

[0197] Synthesis of Compound 69

[0198] Accurately weigh Compound 67-4 (11.5 g, 10 mmol), Compound 69-1 (4.3 g, 22 mmol), and 2.5 ml of pyridine, and sequentially add them into a 500-ml three-necked flask. Then add 200 ml of chloroform. After displacing argon three times, heat the mixture to 60 °C and react for 12 h. Cool to room temperature and distill off the excess solvent under reduced pressure. Wash the crude product with 100 ml of methanol, filter, dissolve the filter cake in dichloromethane, mix it with silica gel for column chromatography, and use PE:DCM = 4:1 (volume ratio) as the eluent to obtain about 9.4 g of Compound 69, with a yield of 62%. MS: 1508.69.

[0199] Example 8: Synthesis of Compound 74

[0200]

[0201] Synthesis of Compound 74-1

[0202] Accurately weigh Compound 67-2 (31.2 g, 30 mmol), Compound 37-3 (15.4 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and sequentially add them into a 1000-ml three-necked flask. Then add 450 ml of anhydrous toluene. After displacing argon three times, heat the mixture to 110 °C and react for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract it three times with ethyl acetate, combine the organic phases, dry them with anhydrous sodium sulfate, and distill off the excess solvent under reduced pressure. Perform silica gel column chromatography with PE:EA = 9:1 (volume ratio) as the eluent to obtain about 29.4 g of Compound 74-1, with a yield of 83%.

[0203] Synthesis of Compound 74-2

[0204] Accurately weigh compound 74-1 (17.7 g, 15 mmol), add it to a 500 ml three-necked flask, add 200 ml of anhydrous DMF. After replacing argon three times, cool it to 0 °C in an ice-salt bath. Weigh phosphorus oxychloride (14.7 g, 96 mmol) and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat up to 80 °C and react for 12 h. Cool to room temperature, pour the reaction solution into water to quench it, extract it three times with dichloromethane, combine the organic phases, dry them with anhydrous sodium sulfate, and remove the excess solvent by reduced pressure distillation. Add silica gel to mix and perform column chromatography. The eluent is PE:DCM = 8:1 (volume ratio) to obtain about 14.3 g of compound 74-2, yield: 77%.

[0205] Synthesis of Compound 74

[0206] Accurately weigh compound 74-2 (12.4 g, 10 mmol), compound 1-7 (5.1 g, 22 mmol), and 2.5 ml of pyridine, and add them successively to a 500 ml three-necked flask. Add 200 ml of chloroform, replace argon three times, and then heat up to 60 °C and react for 12 h. Cool to room temperature and remove the excess solvent by reduced pressure distillation. Wash the crude product with 100 ml of methanol, filter it, dissolve the filter cake with dichloromethane, add silica gel to mix and perform column chromatography. The eluent is PE:DCM = 6:1 (volume ratio) to obtain about 11.8 g of compound 74, yield: 71%. MS: 1662.79.

[0207] Example 9: Synthesis of Compound 114

[0208]

[0209] Synthesis of Compound 114-2

[0210] Accurately weigh compound 114-1 (21.8 g, 50 mmol), compound 19-1 (40.2 g, 50 mmol), and 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (1.83 g, 2.5 mmol), and add them successively to a 1000 ml three-necked flask. Add 400 ml of anhydrous toluene, replace argon three times, and then heat up to 80 °C and react for 12 h. Cool to room temperature and remove the excess solvent by reduced pressure distillation. Dissolve the crude product with dichloromethane, add silica gel to mix and perform column chromatography. The eluent is PE:DCM = 7:1 (volume ratio) to obtain about 35.2 g of compound 114-2, yield: 81%.

[0211] Synthesis of Compound 114-3

[0212] Accurately weigh Compound 114-2 (26.1 g, 30 mmol), Compound 6-1 (16.2 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (3.4 g, 3 mmol), and add them successively to a 1000 ml three-necked flask. Add 450 ml of anhydrous toluene, replace argon three times, and then heat to 110 °C and react for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Column chromatography with silica gel as the stationary phase, and the eluent is PE:EA = 5:1 (volume ratio) to obtain about 23.8 g of Compound 114-3, yield: 76%.

[0213] Synthesis of Compound 114-4

[0214] Accurately weigh Compound 114-3 (15.6 g, 15 mmol), add it to a 500 ml three-necked flask, add 200 ml of anhydrous DMF, replace argon three times, then cool to 0 °C in an ice-salt bath, weigh phosphorus oxychloride (14.7 g, 96 mmol) and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat to 80 °C and react for 12 h. Cool to room temperature, pour the reaction solution into water to quench the reaction, extract three times with dichloromethane, combine the organic phases, dry with anhydrous sodium sulfate, and remove the excess solvent by distillation under reduced pressure. Add silica gel for column chromatography, and the eluent is PE:DCM = 6:1 (volume ratio) to obtain about 13.3 g of Compound 114-4, yield: 81%.

[0215] Synthesis of Compound 114

[0216] Accurately weigh Compound 114-4 (11.0 g, 10 mmol), Compound 114-5 (4.9 g, 22 mmol), and 2.5 ml of pyridine, and add them successively to a 500 ml three-necked flask. Add 200 ml of chloroform, replace argon three times, and then heat to 60 °C and react for 12 h. Cool to room temperature, and remove the excess solvent by distillation under reduced pressure. Wash the crude product with 100 ml of methanol, filter, dissolve the filter cake in dichloromethane, add silica gel for column chromatography, and the eluent is PE:DCM = 6:1 (volume ratio) to obtain about 10.4 g of Compound 114, yield: 69%. MS: 1506.70.

[0217] Example 10: Synthesis of Compound 103

[0218]

[0219] Synthesis of Compound 103-2:

[0220] Accurately weigh Compound 103-1 (24.6 g, 50 mmol), Compound 1-2 (34.6 g, 50 mmol), and 1,1-bis(diphenylphosphino)ferrocene palladium dichloride (1.83 g, 2.5 mmol), and sequentially add them to a 1000 ml three-necked flask. Add 400 ml of anhydrous toluene, replace argon three times, and then heat to 80 °C for reaction for 12 h. Cool to room temperature and distill off the excess solvent under reduced pressure. Dissolve the crude product in dichloromethane, add silica gel for sample mixing, and perform column chromatography. The eluent is PE:DCM = 7:1 (volume ratio) to obtain approximately 30.9 g of Compound 103-2, yield: 76%.

[0221] Synthesis of Compound 103-3

[0222] Accurately weigh Compound 103-2 (24.4 g, 30 mmol), Compound 37-3 (15.4 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (3.4 g, 3 mmol), and sequentially add them to a 1000 ml three-necked flask. Add 450 ml of anhydrous toluene, replace argon three times, and then heat to 110 °C for reaction for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, and distill off the excess solvent under reduced pressure. Perform silica gel sample mixing column chromatography. The eluent is PE:EA = 7:1 (volume ratio) to obtain approximately 23.0 g of Compound 103-3, yield: 80%.

[0223] Synthesis of Compound 103-4

[0224] Accurately weigh Compound 103-3 (14.4 g, 15 mmol), add it to a 500 ml three-necked flask, add 200 ml of anhydrous DMF, replace argon three times, then cool to 0 °C in an ice-salt bath. Weigh phosphorus oxychloride (14.7 g, 96 mmol) and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat to 80 °C for reaction for 12 h. Cool to room temperature, pour the reaction solution into water for quenching, extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and distill off the excess solvent under reduced pressure. Add silica gel for sample mixing and perform column chromatography. The eluent is PE:DCM = 5:1 (volume ratio) to obtain approximately 11.3 g of Compound 103-4, yield: 74%.

[0225] Synthesis of Compound 103

[0226] Accurately weigh Compound 103-4 (10.1 g, 10 mmol), Compound 103-5 (5.6 g, 22 mmol), and 2.5 ml of pyridine, and successively add them to a 500-ml three-necked flask. Then add 200 ml of chloroform, displace argon three times, and heat to 60 °C for reaction for 12 h. Cool to room temperature and distill off the excess solvent under reduced pressure. The crude product is washed with 100 ml of methanol, filtered, and the filter cake is dissolved in dichloromethane and added with silica gel for column chromatography. The eluent is PE:DCM = 4:1 (volume ratio), and about 10.9 g of Compound 103 is obtained, with a yield of 73%. MS: 1490.68.

[0227] Example 11: Synthesis of Compound 100

[0228]

[0229]

[0230] Synthesis of Compound 100-3:

[0231] Accurately weigh Compound 100-1 (24.6 g, 50 mmol), Compound 100-2 (34.6 g, 50 mmol), and 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (1.83 g, 2.5 mmol), and successively add them to a 1000-ml three-necked flask. Then add 400 ml of anhydrous toluene, displace argon three times, and heat to 80 °C for reaction for 12 h. Cool to room temperature and distill off the excess solvent under reduced pressure. The crude product is dissolved in dichloromethane and added with silica gel for column chromatography. The eluent is PE:DCM = 8:1 (volume ratio), and about 31.3 g of Compound 100-3 is obtained, with a yield of 77%.

[0232] Synthesis of Compound 100-4

[0233] Accurately weigh Compound 100-3 (24.4 g, 30 mmol), Compound 1-4 (12.9 g, 30 mmol), and palladium tetrakis(triphenylphosphine) (1.7 g, 1.5 mmol), and successively add them to a 1000-ml three-necked flask. Then add 450 ml of anhydrous toluene, displace argon three times, and heat to 110 °C for reaction for 12 h. Cool to room temperature, pour the reaction solution into 500 ml of an aqueous potassium fluoride solution with a concentration of 0.2 g / ml, extract it three times with ethyl acetate, combine the organic phases, dry them with anhydrous sodium sulfate, and distill off the excess solvent under reduced pressure. Column chromatography with silica gel, and the eluent is PE:EA = 6:1 (volume ratio), and about 21.2 g of Compound 100-4 is obtained, with a yield of 81%.

[0234] Synthesis of Compound 100-5

[0235] Accurately weigh 13.1 g (15 mmol) of compound 100-4 and add it to a 500-ml three-necked flask. Add 200 ml of anhydrous DMF. After displacing argon three times, cool the mixture to 0 °C in an ice-salt bath. Weigh 14.7 g (96 mmol) of phosphorus oxychloride and slowly add it dropwise to the reaction system. After the addition is complete, stir at 0 °C for 1 h, then heat to 80 °C and react for 12 h. Cool to room temperature, pour the reaction solution into water for quenching, extract three times with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, and remove the excess solvent by rotary evaporation under reduced pressure. Add silica gel for sample mixing and perform column chromatography. The eluent is PE:DCM = 4:1 (volume ratio) to obtain approximately 10.6 g of compound 100-5, with a yield of 76%.

[0236] Synthesis of Compound 100

[0237] Accurately weigh 9.29 g (10 mmol) of compound 100-5, 5.1 g (22 mmol) of compound 1-7, and 2.5 ml of pyridine, and sequentially add them to a 500-ml three-necked flask. Add 200 ml of chloroform. After displacing argon three times, heat to 60 °C and react for 12 h. Cool to room temperature and remove the excess solvent by rotary evaporation under reduced pressure. Wash the crude product with 100 ml of methanol, filter, dissolve the filter cake in dichloromethane, add silica gel for sample mixing and perform column chromatography. The eluent is PE:DCM = 3:1 (volume ratio) to obtain approximately 10.6 g of compound 100, with a yield of 78%. MS: 1354.15.

[0238] Fabrication and Characterization of OPV Devices

[0239] The preparation process of the OPV device including the above compound will be described in detail through specific examples below. The structure of the OPV device is as follows: indium tin oxide ITO / PEDOT:PSS / active layer / PFN-Br / Ag

[0240] The preparation steps of Device Example 1 are as follows:

[0241] 1) Cleaning of ITO substrate:

[0242] Clean the ITO conductive glass anode layer, then ultrasonically clean it with deionized water, acetone, and isopropanol for 15 minutes, and then treat it in a plasma cleaner for 5 minutes to improve the work function of the electrode.

[0243] 2) Preparation of anode buffer layer

[0244] Spin-coat PEDOT:PSS uniformly on ITO in air at a spinning speed of 3000 - 4000 rpm and dry it at 150 °C for 15 min to obtain an anode modification layer with a thickness of 20 nm.

[0245] 3) Preparation of photoactive layer

[0246] In a glove box (inert gas atmosphere), the photoactive layer material was spin-coated uniformly on the anode buffer layer at a speed of 1800 - 4000 rpm to obtain an active material layer with a thickness of 100 nm; wherein the donor material in the photoactive layer material is selected from PM6; the acceptor material is selected from Compound 1; the mass ratio of the donor material to the acceptor material is 1:1.2;

[0247] 4) Preparation of the cathode buffer layer

[0248] After thermal annealing on a hot stage at 100 °C for 10 min, the cathode buffer layer material PFN-Br was spin-coated uniformly on the active layer at a spin-coating speed of 1800 - 4000 rpm to obtain a cathode buffer layer with a thickness of 5 nm;

[0249] 5) Preparation of the cathode layer

[0250] In a high vacuum (1×10 -6 mbar), Ag was evaporated onto the cathode buffer layer to form a cathode layer with a thickness of 100 nm.

[0251] 6) Encapsulation

[0252] The device was encapsulated with ultraviolet curable resin in a nitrogen glove box.

[0253]

[0254] Compound REF:

[0255]

[0256] Synthetic route reference: Huang, H., Guo, Q., Feng, S. et al. Noncovalently fused-ring electron acceptors with near-infrared absorption for high-performance organic solar cells. Nat Commun 10, 3038 (2019).

[0257] Device Example 2: The preparation method is the same as that of Device Example 1, except that: the acceptor material Compound 1 is changed to Compound 6;

[0258] Device Example 3: The preparation method is the same as that of Device Example 1, except that: the acceptor material Compound 1 is changed to Compound 19;

[0259] Device Example 4: The preparation method is the same as that of Device Example 1, except that: the acceptor material Compound 1 is changed to Compound 37;

[0260] Device Example 5: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound 46;

[0261] Device Example 6: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound 67;

[0262] Device Example 7: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound 69;

[0263] Device Example 8: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound 74;

[0264] Device Example 9: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound 100;

[0265] Device Example 10: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound 103;

[0266] Device Example 11: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound 114;

[0267] Device Example REF: The preparation method is the same as that of Device Example 1, except that the acceptor material compound 1 is changed to compound REF.

[0268] The performance of the prepared organic solar cell devices was tested. Under the standard light irradiation of AM1.5G by a solar simulator (SS-F5-3A), the current-voltage curves of the cells were tested, and the photoelectric conversion efficiency was calculated as shown in Table 1:

[0269] Table 1

[0270] Device Embodiment Acceptor Material Photovoltaic Conversion Efficiency (%) Device Embodiment 1 Compound 1 15.75 Device Embodiment 2 Compound 6 16.03 Device Embodiment 3 Compound 19 17.07 Device Embodiment 4 Compound 37 16.16 Device Embodiment 5 Compound 46 16.01 Device Embodiment 6 Compound 67 15.45 Device Embodiment 7 Compound 69 15.23 Device Embodiment 8 Compound 74 16.42 Device Embodiment 9 Compound 100 14.99 Device Embodiment 10 Compound 103 15.17 Device Embodiment 11 Compound 114 15.31 Device Embodiment REF Compound REF 12.82

[0271] From the data in Table 1, it can be seen that when used as an acceptor material in organic solar cell devices according to the present invention, the photoelectric conversion efficiency is better than that of the prior art. The reasons are as follows: ① The organic compound described in the present invention has an asymmetric structure, which has a relatively high molecular dipole moment, enhancing the charge transfer between molecules, thereby improving the charge transport ability of the material; ② The organic compound described in the present invention regulates the molecular morphology through S-O covalent bonds, improving the rigidity and planarity of the molecules; the coplanar main chain promotes the intermolecular interaction and the π-π stacking beneficial to charge transport. Thus, good device efficiency is achieved; ③ The organic compound described in the present invention has appropriate HOMO and LUMO energy levels, which is convenient for charge separation and transport when paired with the donor material.

[0272] Meanwhile, it can be seen from the device data that the photoelectric conversion efficiency of Device Examples 2-5 and Device Example 8 has exceeded 16%. The reason is that in the present invention, alkyl substitution is carried out at the R6 and R8 sites. By alkyl substitution, the steric hindrance of the molecule is increased, and the planarity of the molecule is further regulated. At the same time, alkyl substitution also further modifies the molecular morphology and regulates the solubility and film-forming property of the molecule.

[0273] The above examples further illustrate the content of the present application, but should not be construed as a limitation of the present application. Without departing from the spirit and essence of the present application, the modifications and substitutions made to the methods, steps or conditions of the present application all belong to the scope of the present application. If not specifically specified, the technical means used in the examples are conventional means well-known to those skilled in the art.

Claims

1. An organic compound, characterized in that: It has a structure represented by the general formula (II-1) or (II-2): Wherein: R 11 -R 12 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; In the general formula (II-1), R2 is selected from -H; In the general formula (II-2), R3 is selected from -H; R4 is selected from -H; R5, R6, R7, and R8 are selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a branched-chain alkyl group having 3 to 20 C atoms; Y is selected from CR9R 10 ; R9-R 10 Selected from: straight-chain alkyl groups having 1 to 20 C atoms, branched-chain alkyl groups having 3 to 20 C atoms; The said Independently selected from the following groups: Wherein: * represents the connection site; Each occurrence of W is independently selected from S; R 13 Each occurrence is independently selected from: -H, -D, methyl, -Cl, -Br, -F or -I.

2. The organic compound according to claim 1, characterized in that: R7 and R8 are selected from: -H, -D, a straight-chain alkyl group having 1 to 15 C atoms, or a branched-chain alkyl group having 3 to 15 C atoms.

3. The organic compound according to claim 1, characterized in that: R6 is selected from: a straight-chain alkyl group having 1 to 12 C atoms, or a branched-chain alkyl group having 3 to 12 C atoms.

4. The organic compound according to claim 1, wherein: The organic compound is selected from the following structures:

5. A mixture, characterized in that: The mixture contains the organic compound according to any one of claims 1-4, and At least one other organic functional material, and the at least one other organic functional material is selected from an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material.

6. A composition, characterized in that: The composition contains the organic compound according to any one of claims 1-4 or the mixture according to claim 5, and at least one organic solvent.

7. An organic electronic device comprising at least one functional layer, characterized in that: The functional layer material is selected from the organic compound according to any one of claims 1-4 or the mixture according to claim 5 or is prepared from the composition according to claim 6.

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