CN115873024A - A kind of polycyclic organic compound and its application in organic electronic devices - Google Patents

Abstract

The invention relates to a condensed ring organic compound and application thereof in an organic electronic device. The molecule core of the condensed ring organic compound has a larger condensed ring core, which is beneficial to the accumulation among molecules, thereby promoting the effective transmission and collection of charges, and being capable of helping the organic electronic device to improve the photoelectric conversion efficiency when being used as an electron acceptor material.

Description

A condensed ring organic compound and its application in organic electronic devices

Technical Field

The invention relates to the field of organic electronic device materials, in particular to a condensed-ring organic compound and its application in organic electronic devices.

Background Art

Organic solar cells (OPV) have attracted widespread attention worldwide due to their advantages such as low cost, light weight, simple preparation process and large-area flexible preparation. Organic photovoltaic (OPV) cells are generally composed of five parts: anode, anode buffer layer, active layer, cathode buffer layer and cathode. The active layer generally contains donor materials and acceptor materials. Its working principle is: when sunlight passes through the transparent substrate and electrode and enters the active layer, the donor and acceptor materials absorb photons with energy greater than their band gap energy, and electrons are excited to transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), and corresponding holes are generated at the HOMO. Due to the small relative dielectric constant of organic materials, electrons and holes at this time exist in the bound exciton state. Afterwards, the excitons diffuse to the donor-acceptor interface, and driven by 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 transmitted along the continuous channels of the donor and acceptor materials to the anode and cathode respectively, and are collected by the electrodes and output to the external circuit to form current. From the above, we can see that the selection of active layer materials is crucial to the efficiency of organic solar cell devices.

In the early and middle stages of the development of organic solar cells, fullerenes and their derivatives, represented by PC61BM and PC71BM, dominated the electron acceptor materials due to their high electron affinity, isotropic electron transfer ability and high electron mobility. This stage is often 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 adjustability, which limits the efficiency improvement of organic solar cells. Compared with traditional fullerene acceptors, non-fullerene acceptors have attracted widespread attention from the scientific community due to their strong absorption in the visible and near-infrared regions and easy regulation of spectral energy levels. Therefore, in order to further improve the efficiency and stability of organic solar cells, it is crucial to develop new high-performance non-fullerene acceptor materials.

Summary of the invention

The purpose of the present invention is to provide a condensed-ring organic compound, which is used as a small molecule receptor material in an organic solar cell and can help the organic photovoltaic device improve the photoelectric conversion efficiency.

To achieve the purpose of the present invention, the technical solution is specifically as follows:

A condensed ring organic compound having a structure as shown in the general formula (I):

in:

Ar ₁ and Ar ₂ are independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, or substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms;

X is independently selected at each occurrence from O or C(CN) ₂ ;

Y is selected from O, S, Se or NR ₉ ;

Each occurrence of Z is independently selected from N or CR ₁₀ ;

R ₁ to R ₁₀ are each independently selected from: -H, -D, a linear alkyl group having 1 to 20 C atoms, a linear alkoxy group having 1 to 20 C atoms, a linear 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 haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amine group, -CF ₃ , -OCF ₃ , -Cl, -Br, -F, -I, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, an aryloxy group having 6 to 50 ring atoms, a heteroaryloxy group having 5 to 50 ring atoms, or a group formed by a combination of the above groups;

Wherein, two adjacent groups among R ₁ -R ₄ may or may not form a ring.

Correspondingly, the present invention also provides a mixture, comprising the above-mentioned condensed ring organic compound and at least one organic functional material, wherein the organic functional material is selected from anode buffer layer material, cathode buffer layer material, active layer donor material, or active layer acceptor material.

Correspondingly, the present invention also provides an electron acceptor material, wherein the electron acceptor material is selected from the condensed ring organic compound or mixture as described above.

Correspondingly, the present invention also provides an organic electronic device, comprising at least one functional layer, wherein the material of the functional layer is the above-mentioned condensed-ring organic compound or the above-mentioned mixture.

Compared with the prior art, the present invention has the following significant advantages: the core of the condensed ring organic compound provided by the present invention has a larger condensed ring core, which is more conducive to the stacking of molecules, thereby promoting the effective transmission and collection of charges and improving the photoelectric conversion efficiency of the device.

DETAILED DESCRIPTION

The present application provides a condensed ring organic compound and its application in an organic electronic device. To make the purpose, technical solution and effect of the present application clearer and more specific, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

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

In the present invention, organic photovoltaic device and organic solar cell have the same meaning and can be interchangeable.

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

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

In the present invention, "heteroatom" refers to non-carbon atoms, and may be N atom, O atom, S atom or the like.

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

In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, then R can be independently selected from different groups.

In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it should be understood that the defined group may be substituted by one or more substituents R, wherein R is selected from but not limited to: deuterium atom, cyano, isocyano, nitro or halogen, alkyl 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", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and the above groups may be further substituted by substituents acceptable in the art; it is understandable that R' and R" in -NR'R" are independently selected from but not limited to: H, deuterium, 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 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted by substituents acceptable in the art.

In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below unless otherwise specified. 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 thienyl group is 5.

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

"Heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" means a heteroaryl having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl group is optionally further substituted, and suitable examples include but are not limited to: thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, Triazine, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothiophenyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridyl, quinazolinone, dibenzothiophenyl, dibenzofuranyl, carbazolyl and derivatives thereof.

In the present invention, "alkyl" may represent a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 15 or 1 to 6. A phrase containing this term, for example, "C1-9 alkyl" means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or C9 alkyl. Non-limiting examples of alkyl groups 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-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyl decyl, 2-ethyldecyl, 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-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, 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, and the like.

"Amine" refers to an amine derivative having the structural features of the formula -N(X) ₂ , wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, etc. Non-limiting types of amine groups include _-NH2 , -N(alkyl) ₂ , -NH(alkyl), -N(cycloalkyl) ₂ , -NH(cycloalkyl), -N(heterocyclyl) ₂ , -NH(heterocyclyl), _-N (aryl)2, -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclyl), -N(cycloalkyl)(heterocyclyl), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

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

The term "alkoxy" refers to a group having a structure of "-O-alkyl", i.e., an alkyl group as defined above is connected to other groups via an oxygen atom. Phrases containing the term, suitable examples include, but are not limited to, methoxy (-O-CH or -OMe), ethoxy (-O-CHCH or -OEt) and tert-butoxy (-O-C(CH) or -OtBu).

The term "alkylthio" refers to a group having a structure of "-S-alkyl", i.e., an alkyl group as defined above is connected to other groups via a sulfur atom. Phrases containing the term, suitable examples include, but are not limited to: methylthio (-S-CH or -SMe), ethylthio (-S-CHCH or -SEt) and tert-butylthio (-S-C(CH) or -StBu).

In the present invention, "*" connected to a single bond indicates a connection or fusion site;

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

苯环上6个R可以彼此相同或不同。In the present invention, when a group contains multiple substituents with the same symbol, the substituents may be the same or different from each other.

The six Rs on the benzene ring may be the same as or different from each other.

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

In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

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

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

A condensed ring organic compound having a structure as shown in the general formula (I):

in:

Ar ₁ and Ar ₂ are independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, or substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms;

X is independently selected at each occurrence from O or C(CN) ₂ ;

Y is selected from O, S, Se or NR ₉ ;

Each occurrence of Z is independently selected from N or CR ₁₀ ;

R ₁ to R ₁₀ are each independently selected from: -H, -D, a linear alkyl group having 1 to 20 C atoms, a linear alkoxy group having 1 to 20 C atoms, a linear 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 haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amine group, -CF ₃ , -OCF ₃ , -Cl, -Br, -F, -I, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, an aryloxy group having 6 to 50 ring atoms, a heteroaryloxy group having 5 to 50 ring atoms, or a group formed by a combination of the above groups;

Wherein, two adjacent groups among R ₁ -R ₄ may or may not form a ring.

In one embodiment, R ₁ -R ₁₀ are independently selected from: -H, -D, a linear alkyl group having 1 to 20 C atoms, a linear alkoxy group having 1 to 10 C atoms, a linear alkylthio group having 1 to 10 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 10 C atoms, a cyano group, an isocyano group, a hydroxyl group, a nitro group, -CF ₃ , -OCF ₃ , -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, an aryloxy group having 6 to 30 ring atoms, a heteroaryloxy group having 5 to 30 ring atoms, or a group formed by a combination of the above groups; wherein two adjacent groups in R ₁ -R ₄ may or may not form a ring with each other.

In one embodiment, Ar ₁ and Ar ₂ are independently selected from substituted or unsubstituted aromatic groups having 6-10 ring atoms, or substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms. Specifically, Ar ₁ and Ar ₂ are independently selected from the following groups:

in:

* indicates fusion site;

Each occurrence of V is independently selected from N or CR ₁₁ ;

W, at each occurrence, is independently selected from O, S, Se, CR ₁₁ R ₁₂ or NR ₁₂ ;

R ₁₁ -R ₁₂ are 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 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 a combination of the above groups.

In one embodiment, R ₁₁ -R ₁₂ are independently selected from: -H, -D, a linear alkyl group having 1 to 10 C atoms, or a branched alkyl group having 3 to 10 C atoms.

In one embodiment, the general formula (I) is selected from the general formula (II-1), (II-2) or (II-3):

In one embodiment, Z is independently selected from CH or N; further, each occurrence of Z in Formula (I), Formula (II-1), (II-2) or (II-3) is selected from the same group.

In a more preferred embodiment, the general formula (I) is selected from the following structures of the general formulae (III-1) to (III-6):

In one embodiment, if two adjacent groups among R ₁ -R ₄ form a ring with each other, preferably a 6-membered ring; further, two adjacent groups among R ₁ -R ₄ form a substituted or unsubstituted 6-membered benzene ring with each other.

每次出现，独立选自结构式(B-1)、(B-2)或(B-3)：In one embodiment,

Each occurrence is independently selected from structural formula (B-1), (B-2) or (B-3):

* indicates the attachment site.

In one embodiment, R ₁ -R ₄ are independently selected from: -H, -D, a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 10 carbon atoms, cyano, isocyano, hydroxyl, nitro, -CF ₃ , -Cl, -Br, -F, -I, or a combination thereof.

In one embodiment, R ₁ -R ₄ are independently selected from: -H, -D, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, cyano, isocyano, hydroxyl, nitro, -CF ₃ , -Cl, -Br, -F, or -I, or a combination thereof.

每次出现，独立选自(C-1)至(C-60)以下结构式：In a specific embodiment,

Each occurrence is independently selected from the following structural formulas (C-1) to (C-60):

Wherein: * indicates the connection site.

Preferably, _{R5- R8} are independently selected from -H, -D, or a linear alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, or a group formed by a combination of the above groups. More preferably, _R5 and _R6 are selected from the same group; _R7 - _R8 are selected from the same group.

In one embodiment, R ₉ is selected from a linear alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms.

In one embodiment, the “straight-chain alkyl group having 1 to 20 carbon atoms” is selected from methyl, ethyl, C ₈ H ₁₇ , C ₆ H ₁₃ , C ₅ H ₁₁ , C ₁₁ H ₂₃ , and C ₁₂ H ₂₅ ; the “branched-chain alkyl group having 3 to 20 carbon atoms” is selected from tert-butyl, isopropyl,

In one embodiment, the “straight-chain alkyl group having 1 to 10 carbon atoms” is selected from methyl, ethyl, C ₈ H ₁₇ , C ₆ H ₁₃ , and C ₅ H ₁₁ ; the “branched-chain alkyl group having 3 to 20 carbon atoms” is selected from tert-butyl, isopropyl,

More specifically, the fused ring organic compound described in the present application can be selected from but not limited to the following structural formula:

The condensed-ring 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.

The present invention also relates to a mixture, comprising at least one organic compound as described above, and at least another organic functional material, wherein the at least another organic functional material can be selected from anode buffer layer material, cathode buffer layer material, active layer donor material, or active layer acceptor material. The weight ratio of the at least another organic functional material to the another acceptor 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 of the donor material/acceptor material is 1/1.2.

In one embodiment, the another organic functional material is selected from an active layer donor material or an active layer acceptor material.

The present application further relates to an electron acceptor material, wherein the electron acceptor material is selected from the condensed-ring organic compound or mixture as described above.

The present application further relates to an application of the condensed ring organic compound or mixture as described above in an organic electronic device. The organic electronic device can be selected from, but not limited to, an organic solar cell (OPV), an organic light emitting diode (OLED), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and OPV is particularly preferred.

The present application also relates to an organic electronic device, comprising at least one functional layer, wherein the functional layer comprises the above-mentioned condensed ring organic compound or the above-mentioned mixture. Preferably, the functional layer is selected from an anode buffer layer, an active layer or a cathode buffer layer.

In one embodiment, the organic electronic device comprises at least a first electrode, a second electrode and one or more functional layers 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 anode buffer layers, active layers and cathode buffer layers.

Furthermore, the organic solar cell further comprises a substrate. Specifically, the substrate may be disposed below the first electrode.

In one embodiment, the first electrode is an anode and the second electrode is a cathode; in another embodiment, the first electrode may be a cathode and the second electrode may be an anode.

In one embodiment, as a substrate, a substrate having excellent transparency, surface smoothness, ease of operation and water resistance can be used. Specifically, a glass substrate, a thin film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in a single or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and polyimide (PI), but is not limited thereto, and a substrate commonly used for organic solar cells may also be used.

At least one of the anode electrode and the cathode electrode is made of a transparent or translucent material. The electrode material may 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 with 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 of poly(styrene sulfonate):PSS (poly(3,4-ethylenedioxythiophene)), polypyrrole and polyaniline, etc., but are not limited thereto.

The active layer includes an electron donor material and an electron acceptor material. In the present specification, the active layer material may mean an electron donor material and an electron acceptor material.

Specifically, the electron donor material can be a variety of polymer materials or small molecule materials. The polymer material can be selected from polythiophene material systems, such as P3AT, P3HT, P3OT, P3DDT, etc.; fluorene-containing polymer material systems, such as PF8BT, etc.; novel structure narrow band gap polymer material systems, such as copolymerization of 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, etc. The small molecule material can be selected from one or more of the following: copper phthalocyanine (II), zinc phthalocyanine, tris[4-(5-dicyanomethylenemethyl-2-thienyl)phenyl]amine, 2,4-bis[4-(N,N-dibenzylamino)-2,6-dihydroxyphenyl]squaryl cyanine, benzo[b]anthracene and pentacene, B8, B10, etc.

The photoactive layer may be formed by 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, spray coating, doctor blade, slit coating, and inkjet printing, but is not limited thereto.

The anode buffer layer material can be selected from materials with higher work functions, such as PEDOT:PSS (poly(3,4-ethylenedioxythiophene)) of poly(styrene sulfonic acid), molybdenum oxide (MoOx), vanadium oxide ( _V2O5 ), nickel oxide (NiO), tungsten oxide ( _WOx, preferably, x is selected from 2 or 3), etc., but not _limited thereto.

The cathode buffer layer material may be a low work function material such as metal complexes containing 8-hydroxyquinoline, LiQ, LiF, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs ₂ CO ₃ ), and polymers such as PFN-Br or PFN, but is not limited thereto.

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, automobiles and building integrated photovoltaics (BIPV), electronic price tags, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

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

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

Example 1: Synthesis of Compound 4:

Synthesis of compound 1-1:

Accurately weigh compound 6,7-dinitroquinoxaline-2,3-diamine (25g, 100mmol) and triethylamine (20.2g, 200mmol) and add them to a 1000mL three-necked flask in sequence, add 350mL of anhydrous dichloromethane, pump and fill with nitrogen three times, stir at room temperature for half an hour, then cool the reaction system to 0°C, slowly add thionyl chloride (14.3g dissolved in 150mL of dichloromethane), and keep the temperature at 0°C. After the addition is complete, heat and reflux for 3 hours. After the reaction is completed, slowly pour the reaction solution into dilute hydrochloric acid, then extract it three times with dichloromethane, combine the organic phases, dry it with anhydrous sodium sulfate, and distill it under reduced pressure to remove the excess solvent. The crude product is slurried with petroleum ether to obtain about 19g of compound 1-2. Yield: 68.3%. Ms: 278.02

Synthesis of compound 1-2:

Accurately weigh compound 1-1 (19 g, 68 mmol) and add it to a 500 mL three-necked flask, add ethyl acetate 200 mL, pump and fill with nitrogen three times, then add stannous chloride dihydrate (31 g, 136 mmol), heat and reflux for 2 hours, after the raw materials react completely, wash with water, extract with ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, and remove excess solvent by vacuum distillation to obtain about 10.8 g of compound 1-2, with a yield of 72.8%. Ms: 218.42 Synthesis of compound 1-4:

Accurately weigh compound 5-(bromomethyl)-11-alkane (49.8g, 200mmol) and magnesium chips (7.2g, 300mmol) and add them to a 1000mL three-necked flask in turn, add about 300mL of anhydrous tetrahydrofuran, pump and fill with nitrogen three times, add a single iodine, then heat the reaction system to 60°C, and place the reaction system at room temperature after obvious bubbles appear on the surface of the magnesium chips. After the raw materials are basically reacted, slowly drop compound 1-3 (29.8g, 100mmol dissolved in 150mL of anhydrous tetrahydrofuran) into the reaction system, and heat to 60°C after the addition is complete. After the reaction is complete, add water to quench, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, and silica gel column chromatography, eluent is n-hexane to obtain about 19.3g of compound 1-4. Yield: 49.8%. Ms: 388.37

Synthesis of compound 1-5:

Accurately weigh compound 1-2 (4.4 g, 20 mmol), compound 1-4 (15.5 g, 40 mmol), tris(dibenzylideneacetone)dipalladium (0.2 g, 0.4 mmol), sodium tert-butoxide (5.8 g, 60 mmol), and add them to a 500 mL three-necked flask in sequence. Add about 200 mL of anhydrous toluene, evacuate and fill with nitrogen three times, then add 0.34 mL of tri-tert-butylphosphine in toluene (mass ratio 10%, that is, assuming that every 100 mL of toluene contains 10 g of tri-tert-butylphosphine) solution, then heat to 100 ° C and react for 12 hours. After the reaction is completed, cool to room temperature, dilute with water and extract with ethyl acetate. The organic phases are combined, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, the eluent volume ratio is PE:EA = 10:1 (volume ratio) to obtain about 10.6 g of compound 1-5.

Yield: 63.8%. Ms: 832.05

Synthesis of compound 1-6:

Accurately weigh compound 1-5 (10g, 12mmol) and add it to a 500mL three-necked flask, add about 50mL of anhydrous dichloromethane, pump and fill with nitrogen three times, then cool to about 0°C, slowly drop NBS (8.9g, 50mmol dissolved in 200mL of dichloromethane) in dichloromethane solution to the reaction system, and heat to reflux for 3 hours after the addition is complete. After the raw material is completely reacted, cool to room temperature, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is n-hexane to obtain about 11.5g of compound 1-6. Yield 83.6%. Ms: 1147.51

Synthesis of compound 1-7:

Accurately weigh compound 1-6 (11.5 g, 10 mmol) and add it to a 250 mL three-necked flask, add about 100 mL of anhydrous xylene, add palladium acetate (0.13 g, 0.5 mmol), potassium carbonate (4.1 g, 30 mmol), pump and fill with nitrogen three times, then heat to 30 ° C and react for 6 hours. After the raw materials are completely reacted, cool to room temperature, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE: EA = 10: 1 (volume ratio), and obtain about 7.8 g of compound 1-7. Yield: 79.2%. Ms: 986.16

Synthesis of compound 1-8:

Accurately weigh compound 1-7 (6.9 g, 7 mmol) and add it to a 250 mL three-necked flask, add about 80 mL of anhydrous DMF, pump and fill with nitrogen three times, then slowly add sodium hydrogen (60% 0.8 g) to the reaction system, react at room temperature for half an hour, then add isooctane bromide (4.1 g, 21 mmol), and then heat to 60 ° C for 3 hours. After the raw materials are completely reacted, dilute with water and extract with ethyl acetate. Combine the organic phases, dry them with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel and column chromatography. The eluent is PE:EA=30:1 (volume ratio) to obtain about 7.3 g of compound 1-8, with a yield of 86.2%. Ms: 1210.31

Synthesis of compound 1-9:

Accurately weigh compound 1-8 (7.3g, 6mmol) and add it to a 250mL three-necked flask, add about 80mL of anhydrous THF, evacuate and fill with nitrogen three times, then cool to -80°C, then drop n-butyl lithium (2.5M 7.2mL) into the reaction system, react at low temperature for 2 hours, slowly drop about 2mL of anhydrous DMF into the reaction system, naturally warm to room temperature and react for 1 hour. After the raw materials react completely, add water to quench. After separation, extract with ethyl acetate three times, combine the organic phases, remove excess solvent by vacuum distillation, mix with silica gel for column chromatography, eluent is PE; EA = 20:1 (volume ratio) to obtain about 5.2g of compound 1-9. Yield: 78.2%. Ms: 1108.51

Synthesis of compound 4:

Accurately weigh compound 1-9 (4.4 g, 4 mmol) and compound 1-10 (2.8 g, 12 mmol), add them to a 100 mL three-necked flask in turn, add tert-butyl alcohol 60 mL, piperidine 2 mL, pump and fill with nitrogen three times, heat to 80 ° C and react overnight, remove excess solvent by vacuum distillation after the raw materials are completely reacted, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is PE:DCM=10:1 (volume ratio), obtain about 3.3 g of compound 4, yield: 53.9%. Ms: 1532.24

Example 2: Synthesis of Compound 8

Synthesis of compound 8:

Accurately weigh compound 1-9 (4.4 g, 4 mmol) and compound 2-1 (3.1 g, 12 mmol), add them to a 100 mL three-necked flask in turn, add tert-butyl alcohol 60 mL, piperidine 2 mL, pump and fill with nitrogen three times, heat to 80 ° C and react overnight, remove excess solvent by vacuum distillation after the raw materials are completely reacted, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is PE:DCM=10:1 (volume ratio) to obtain about 3.5 g of compound 8, yield: 55.2%. Ms: 1584.06

Example 3: Synthesis of Compound 31

Synthesis of compound 3-2:

Accurately weigh compound 3-1 (18.8g, 100mmol) and triethylamine (20.2g, 200mmol) and add them to a 1000mL three-necked flask in turn, add 350mL of anhydrous dichloromethane, pump and fill with nitrogen three times, stir at room temperature for half an hour, then cool the reaction system to 0℃, slowly add thionyl chloride (14.3g dissolved in 150mL of dichloromethane), and keep the temperature at 0℃. After the addition is complete, heat and reflux for 3 hours. After the reaction is completed, slowly pour the reaction solution into dilute hydrochloric acid, then extract it three times with dichloromethane, combine the organic phases, dry it with anhydrous sodium sulfate, and then distill it under reduced pressure to remove the excess solvent. The crude product is slurried with petroleum ether to obtain about 15.6g of compound 3-2. Yield: 72.1%. Ms: 217.24

Synthesis of compound 3-3:

Accurately weigh compound 3-2 (4.3g, 20mmol), compound 1-4 (15.5g, 40mmol), tris(dibenzylideneacetone)dipalladium (0.2g, 0.4mmol), sodium tert-butoxide (5.8g, 60mmol), and add them to a 500mL three-necked flask in sequence. Add about 200mL of anhydrous toluene, pump and fill with nitrogen three times, then add 0.34mL of tri-tert-butylphosphine toluene (mass ratio 10%) solution, then heat to 100℃ and react for 12 hours. After the reaction is completed, cool to room temperature, dilute with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel column chromatography, and the eluent is PE:EA＝10:1 to obtain about 10.3g of compound 3-3. Yield 62.1%. Ms:830.13

Synthesis of compound 3-4:

Accurately weigh compound 3-3 (10g, 12mmol) and add it to a 500mL three-necked flask, add about 50mL of anhydrous dichloromethane, pump and fill with nitrogen three times, then cool to about 0°C, slowly drop NBS (8.9g, 50mmol dissolved in 200mL of dichloromethane) in dichloromethane solution to the reaction system, and heat to reflux for 3 hours after the addition is complete. After the raw material is completely reacted, cool to room temperature, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is n-hexane to obtain about 11.6g of compound 3-4. Yield 84.4%. Ms: 1145.81

Synthesis of compound 3-5:

Accurately weigh compound 3-4 (11.5 g, 10 mmol) and add it to a 250 mL three-necked flask, add about 100 mL of anhydrous xylene, add palladium acetate (0.13 g, 0.5 mmol), potassium carbonate (4.1 g, 30 mmol), pump and fill with nitrogen three times, then heat to 30 ° C and react for 6 hours. After the raw materials are completely reacted, cool to room temperature, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, and eluent is PE:EA＝10:1 (volume ratio), to obtain about 7.5 g of compound 3-5. Yield: 76.3%. Ms: 984.05

Synthesis of compound 3-6:

Accurately weigh compound 3-5 (6.9 g, 7 mmol) and add it to a 250 mL three-necked flask, add about 80 mL of anhydrous DMF, pump and fill with nitrogen three times, then slowly add sodium hydrogen (60% 0.8 g) to the reaction system, react at room temperature for half an hour, then add bromoisoctane (4.1 g, 21 mmol), and then heat to 60 ° C for 3 hours. After the raw materials react completely, dilute with water and extract with ethyl acetate. Combine the organic phases, dry them with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel and perform column chromatography. The eluent is PE:EA=30:1 (volume ratio) to obtain about 7.1 g of compound 3-6, with a yield of 84%.

Ms:1208.42

Synthesis of compound 3-7:

Accurately weigh compound 3-6 (7.3g, 6mmol) and add it to a 250mL three-necked flask, add about 80mL of anhydrous THF, evacuate and fill with nitrogen three times, then cool to -80°C, then drop n-butyl lithium (2.5M 7.2mL) into the reaction system, react at low temperature for 2 hours, slowly drop about 2mL of anhydrous DMF into the reaction system, naturally warm to room temperature and react for 1 hour. After the raw materials react completely, add water to quench. After separation, extract with ethyl acetate three times, combine the organic phases, remove excess solvent by vacuum distillation, mix with silica gel for column chromatography, eluent is PE; EA = 20:1 (volume ratio) to obtain about 5.2g of compound 3-7. Yield: 78.4%. Ms: 1106.50

Synthesis of compound 31:

Accurately weigh compound 3-7 (4.4 g, 4 mmol) and compound 3-8 (2 g, 12 mmol), add them to a 100 mL three-necked flask, add tert-butyl alcohol 60 mL, piperidine 2 mL, pump and fill with nitrogen three times, heat to 80 ° C and react overnight, remove excess solvent by vacuum distillation after the raw materials are completely reacted, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is PE:DCM=10:1 (volume ratio) to obtain about 3.3 g of compound 31, yield: 59%. Ms: 1398.71

Example 4: Synthesis of Compound 35

Synthesis of compound 35:

Accurately weigh compound 3-7 (4.4 g, 4 mmol) and compound 4-1 (3.2 g, 12 mmol), add them to a 100 mL three-necked flask, add tert-butyl alcohol 60 mL, piperidine 2 mL, pump and fill with nitrogen three times, heat to 80 ° C and react overnight, remove excess solvent by vacuum distillation after the raw materials are completely reacted, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is PE:DCM=10:1 (volume ratio) to obtain about 3.8 g of compound 35, yield: 59.5%. Ms: 1595.80

Example 5: Synthesis of Compound 54

Synthesis of compound 5-1:

Accurately weigh compound 3-1 (18.8 g, 100 mmol) and add it to a 500 mL three-necked flask, add about 200 mL of glacial acetic acid, cool to 0 ° C and slowly add sodium nitrite (8.28 g, 120 mmol dissolved in 20 mL of water) aqueous solution to the system, stir at room temperature for half an hour after addition, and filter to obtain 18.5 g of crude compound 5-1. Ms: 199.87

Synthesis of compound 5-2:

Accurately weigh compound 5-1 (18.5 g) and add it to a 500 mL three-necked flask, add about 200 mL of DMF, then add sodium hydroxide (6 g, 150 mmol), isooctane bromide (23.2 g, 120 mmol), pump and fill with nitrogen three times, then heat to 60 ° C and react for 4 hours. After the raw materials react completely, dilute with water, extract with ethyl acetate three times, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Silica gel mixed sample column chromatography, eluent (volume ratio) is PE: EA = 3: 1 to obtain about 17.5 g of compound 5-2. Yield: 60.5%. Ms: 312.33

Synthesis of compound 5-4:

Accurately weigh compound 5-2 (6.2g, 20mmol), compound 5-3 (14.9g, 40mmol), tris(dibenzylideneacetone)dipalladium (0.2g, 0.4mmol), sodium tert-butoxide (5.8g, 60mmol), and add them to a 500mL three-necked flask in sequence. Add about 200mL of anhydrous toluene, pump and fill with nitrogen three times, then add 0.34mL of tri-tert-butylphosphine toluene (mass ratio 10%) solution, then heat to 100℃ and react for 12 hours. After the reaction is completed, cool to room temperature, dilute with water, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel column chromatography, and the eluent volume ratio is PE:EA＝10:1 to obtain about 11.7g of compound 5-4. Yield 65.1%. Ms:897.32

Synthesis of compound 5-5:

Accurately weigh compound 5-4 (10.8g, 12mmol) and add it to a 500mL three-necked flask, add about 50mL of anhydrous dichloromethane, pump and fill with nitrogen three times, then cool to about 0°C, slowly drop NBS (8.9g, 50mmol dissolved in 200mL of dichloromethane) in dichloromethane solution to the reaction system, and heat to reflux for 3 hours after the addition is complete. After the raw material is completely reacted, cool to room temperature, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel and column chromatography, eluent is n-hexane to obtain about 12.0g of compound 5-5. Yield 82.7%. Ms: 1212.89

Synthesis of compound 5-6:

Accurately weigh compound 5-5 (12.1 g, 10 mmol) and add it to a 250 mL three-necked flask, add about 100 mL of anhydrous xylene, add palladium acetate (0.13 g, 0.5 mmol), potassium carbonate (4.1 g, 30 mmol), pump and fill with nitrogen three times, then heat to 30 ° C and react for 6 hours. After the raw materials are completely reacted, cool to room temperature, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE: EA = 10: 1 (volume ratio), and obtain about 8.4 g of compound 5-6. Yield: 79.6%. Ms: 1051.17 Synthesis of compound 5-7:

Accurately weigh compound 5-6 (7.3g, 7mmol) and add it to a 250mL three-necked flask, add about 80mL of anhydrous DMF, pump and fill with nitrogen three times, then slowly add sodium hydrogen (60% 0.8g) to the reaction system, react at room temperature for half an hour, then add bromoisoctane (4.1g, 21mmol), and then heat to 60℃ for 3 hours. After the raw materials react completely, dilute with water and extract with ethyl acetate. Combine the organic phases, dry them with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel and perform column chromatography. The eluent is PE:EA=30:1 (volume ratio) to obtain about 7.1g of compound 5-7, with a yield of 80.1%. Ms:1275.56

Synthesis of compound 5-8:

Accurately weigh compound 5-7 (6.4g, 5mmol) and add it to a 250mL three-necked flask, add about 80mL of anhydrous THF, evacuate and fill with nitrogen three times, then cool to -80℃, then drop n-butyl lithium (2.5M 6mL) into the reaction system, react at low temperature for 2 hours, slowly drop about 2mL of anhydrous DMF into the reaction system, naturally warm to room temperature and react for 1 hour. After the raw materials react completely, add water to quench. After separation, extract with ethyl acetate three times, combine the organic phases, remove excess solvent by vacuum distillation, mix with silica gel for column chromatography, eluent is PE; EA = 20:1 (volume ratio) to obtain about 4.7g of compound 5-8. Yield: 79.9%. Ms: 1173.26

Synthesis of compound 54:

Accurately weigh compound 5-8 (4.7 g, 4 mmol) and compound 5-8 (2.3 g, 12 mmol), add them to a 100 mL three-necked flask, add tert-butyl alcohol 60 mL, piperidine 2 mL, pump and fill with nitrogen three times, heat to 80 ° C and react overnight, remove excess solvent by vacuum distillation after the raw materials are completely reacted, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is PE:DCM=10:1 (volume ratio) to obtain about 3.6 g of compound 54, yield: 59.6%. Ms: 1525.32

Example 6: Synthesis of Compound 108

Synthesis of compound 6-2:

Accurately weigh compound 3-2 (4.3g, 20mmol), compound 6-1 (9.9g, 40mmol), tris(dibenzylideneacetone)dipalladium (0.2g, 0.4mmol), sodium tert-butoxide (5.8g, 60mmol), and add them to a 500mL three-necked flask in sequence. Add about 200mL of anhydrous toluene, evacuate and fill with nitrogen three times, then add 0.34mL of toluene solution of tri-tert-butylphosphine (10% by volume), then heat to 100℃ and react for 12 hours. After the reaction is completed, cool to room temperature, dilute with water, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel for column chromatography, and the eluent volume ratio is PE:EA=10:1 (volume ratio) to obtain about 8.5g of compound 6-2. Yield 77.3%. Ms: 550.41

Synthesis of compound 6-3:

Accurately weigh compound 6-2 (8.3 g, 15 mmol) and add it to a 250 mL three-necked flask, add about 100 mL of anhydrous xylene, add palladium acetate (0.13 g, 0.5 mmol), potassium carbonate (4.1 g, 30 mmol), pump and fill with nitrogen three times, then heat to 30 ° C and react for 6 hours. After the raw materials are completely reacted, cool to room temperature, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE: EA = 10: 1 (volume ratio), and obtain about 6.3 g of compound 6-3. Yield: 88.1%. Ms: 477.63

Synthesis of compound 6-4:

Accurately weigh compound 6-3 (5.7g, 12mmol) and add it to a 250mL three-necked flask, add about 80mL of anhydrous DMF, pump and fill with nitrogen three times, then slowly add sodium hydrogen (60% 0.9g) to the reaction system, react at room temperature for half an hour, then add bromoisoctane (4.6g, 24mmol), and then heat to 60℃ for 3 hours. After the raw materials react completely, dilute with water and extract with ethyl acetate. Combine the organic phases, dry them with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel and perform column chromatography. The eluent is PE:EA=30:1 (volume ratio) to obtain about 6.6g of compound 6-4, with a yield of 78.5%. Ms:702.01

Synthesis of compound 6-5:

Accurately weigh compound 6-4 (6.3g, 9mmol) and add it to a 500mL three-necked flask, add about 50mL of anhydrous dichloromethane, pump and fill with nitrogen three times, then cool to about 0°C, slowly drop NBS (3.2g, 18mmol dissolved in 200mL of dichloromethane) in dichloromethane solution to the reaction system, and heat to reflux for 3 hours after the addition is complete. After the raw material is completely reacted, cool to room temperature, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is n-hexane to obtain about 6.3g of compound 6-5. Yield 81.5%. Ms: 859.60

Synthesis of compound 6-6:

Accurately weigh compound 5-(bromomethyl)-11-alkane (3.5g, 14mmol) and magnesium chips (0.5g, 21mmol) and add them to a 1000mL three-necked flask in turn. Add about 300mL of anhydrous tetrahydrofuran, pump and fill with nitrogen three times, then add a single iodine particle, then heat the reaction system to 60°C, wait for obvious bubbles to appear on the surface of the magnesium chips, then place the reaction system at room temperature for reaction, after the raw materials are basically reacted, slowly drop compound 6-5 (6g, 7mmol dissolved in 150mL of anhydrous tetrahydrofuran) into the reaction system, after the addition is complete, heat to 60°C for reaction, after the reaction is complete, add water to quench, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and then remove the excess solvent by vacuum distillation, silica gel column chromatography, eluent is n-hexane to obtain about 4.3g of compound 6-6. Yield: 59.2%. Ms: 1038.53

Synthesis of compound 6-7:

Accurately weigh compound 6-6 (4.2g, 4mmol) and add it to a 500mL three-necked flask, add about 50mL of anhydrous dichloromethane, pump and fill with nitrogen three times, then cool to about 0°C, slowly drop NBS (2.1g, 12mmol dissolved in 200mL of dichloromethane) in dichloromethane solution to the reaction system, and heat to reflux for 3 hours after the addition is complete. After the raw material is completely reacted, cool to room temperature, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is n-hexane to obtain about 4.3g of compound 6-7. Yield 89.9%. Ms: 1196.22

Synthesis of compound 6-8:

Accurately weigh compound 6-7 (3.6g, 3mmol) and add it to a 100mL three-necked flask, add about 40mL of anhydrous THF, evacuate and fill with nitrogen three times, then cool to -80°C, then drop n-butyl lithium (2.5M 1.8mL) into the reaction system, react at low temperature for 2 hours, slowly drop about 2mL of anhydrous DMF into the reaction system, naturally warm to room temperature and react for 1 hour. After the raw materials react completely, add water to quench. After separation, extract with ethyl acetate three times, combine the organic phases, remove excess solvent by vacuum distillation, mix with silica gel column chromatography, eluent is PE; EA = 20:1 (volume ratio) to obtain about 2.6g of compound 6-8. Yield: 79.2%. Ms: 1094.57

Synthesis of compound 108:

Accurately weigh compound 6-8 (2.2 g, 2 mmol) and compound 1-10 (1.4 g, 6 mmol), add them to a 100 mL three-necked flask, add tert-butyl alcohol 40 mL, piperidine 1 mL, pump and fill with nitrogen three times, heat to 80 ° C and react overnight, remove excess solvent by vacuum distillation after the raw materials are completely reacted, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is PE:DCM=10:1 (volume ratio), obtain about 1.8 g of compound 108, yield: 59.3%. Ms: 1518.35

Example 7: Synthesis of Compound 136

Synthesis of compound 7-1:

Accurately weigh compound 3-1 (18.8 g, 100 mmol) and selenium dioxide (11 g, 100 mmol), add them to a 1000 mL three-necked flask in sequence, add 300 mL of anhydrous ethanol, pump and fill with nitrogen three times, then heat to 80 ° C and react for 2 hours. After the raw materials react completely, cool to room temperature, filter, and slurry the filter cake with petroleum ether to obtain about 15.6 g of compound 7-1. Yield: 59.3%. Ms: 263.87

Synthesis of compound 7-2:

Accurately weigh compound 7-1 (10.5g, 40mmol), compound 6-1 (19.8g, 80mmol), tris(dibenzylideneacetone)dipalladium (0.2g, 0.4mmol), sodium tert-butoxide (11.5g, 120mmol), and add them to a 500mL three-necked flask in sequence. Add about 200mL of anhydrous toluene, pump and fill with nitrogen three times, then add 0.34mL of tri-tert-butylphosphine toluene (mass ratio 10%) solution, then heat to 100℃ and react for 12 hours. After the reaction is completed, cool to room temperature, dilute with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel column chromatography, and the eluent volume ratio is PE:EA＝10:1 to obtain about 16.8g of compound 7-2. Yield 70.4%. Ms:597.23

Synthesis of compound 7-3:

Accurately weigh compound 7-2 (11.9 g, 20 mmol) and add it to a 250 mL three-necked flask, add about 100 mL of anhydrous xylene, add palladium acetate (0.26 g, 1 mmol), potassium carbonate (8.3 g, 60 mmol), pump and fill with nitrogen three times, then heat to 30 ° C and react for 6 hours. After the raw materials are completely reacted, cool to room temperature, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE: EA = 10: 1 (volume ratio), and obtain about 8.3 g of compound 7-3. Yield: 79.3%. Ms: 524.38

Synthesis of compound 7-4:

Accurately weigh compound 7-3 (7.9 g, 15 mmol) and add it to a 250 mL three-necked flask, add about 80 mL of anhydrous DMF, pump and fill with nitrogen three times, then slowly add sodium hydrogen (60% 1.7 g) to the reaction system, react at room temperature for half an hour, then add bromoisoctane (5.8 g, 30 mmol), and then heat to 60 ° C for 3 hours. After the raw materials are completely reacted, dilute with water and extract with ethyl acetate. Combine the organic phases, dry them with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Mix the sample with silica gel and column chromatography, and the eluent is PE:EA=30:1 (volume ratio) to obtain about 8.6 g of compound 7-4, with a yield of 76.7%. Ms: 748.88

Synthesis of compound 7-5:

Accurately weigh compound 7-4 (7.5g, 10mmol) and add it to a 500mL three-necked flask, add about 50mL of anhydrous dichloromethane, pump and fill with nitrogen three times, then cool to about 0°C, slowly drop NBS (3.6g, 20mmol dissolved in 200mL of dichloromethane) in dichloromethane solution to the reaction system, and heat to reflux for 3 hours after the addition is complete. After the raw material is completely reacted, cool to room temperature, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel and column chromatography, eluent is n-hexane to obtain about 6.3g of compound 7-5. Yield 69.6%. Ms: 906.51

Synthesis of compound 7-6:

Accurately weigh compound 5-(bromomethyl)-11-alkane (3.5g, 14mmol) and magnesium chips (0.5g, 21mmol) and add them to a 1000mL three-necked flask in turn, add about 300mL of anhydrous tetrahydrofuran, pump and fill with nitrogen three times, add a single iodine, then heat the reaction system to 60°C, wait for obvious bubbles to appear on the surface of the magnesium chips, place the reaction system at room temperature for reaction, wait for the raw materials to react basically, slowly drop compound 7-5 (6.3g, 7mmol dissolved in 150mL of anhydrous tetrahydrofuran) into the reaction system, heat to 60°C for reaction after the addition is complete, add water to quench after the reaction is complete, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, silica gel column chromatography, eluent is n-hexane to obtain about 4.5g of compound 7-6. Yield: 59.3%. Ms: 1085.44

Synthesis of compound 7-7:

Accurately weigh compound 7-6 (4.3g, 4mmol) and add it to a 500mL three-necked flask, add about 50mL of anhydrous dichloromethane, pump and fill with nitrogen three times, then cool to about 0°C, slowly drop NBS (2.1g, 12mmol dissolved in 200mL of dichloromethane) in dichloromethane solution to the reaction system, and heat to reflux for 3 hours after the addition is complete. After the raw material is completely reacted, cool to room temperature, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is n-hexane to obtain about 4.3g of compound 7-7. Yield 86.5%. Ms: 1242.04

Synthesis of compound 7-8:

Accurately weigh compound 7-7 (3.7g, 3mmol) and add it to a 100mL three-necked flask, add about 40mL of anhydrous THF, pump and fill with nitrogen three times, then cool to -80°C, then drop n-butyl lithium (2.5M 1.8mL) into the reaction system, react at low temperature for 2 hours, slowly drop about 2mL of anhydrous DMF into the reaction system, naturally warm to room temperature and react for 1 hour. After the raw material reacts completely, add water to quench. After separation, extract with ethyl acetate three times, combine the organic phases, remove excess solvent by vacuum distillation, mix with silica gel column chromatography, eluent is PE; EA = 20:1 (volume ratio) to obtain about 2.7g of compound 7-8. Yield: 78.9%. Ms: 1140.50

Synthesis of compound 136:

Accurately weigh compound 7-8 (2.3g, 2mmol) and compound 5-9 (1.2g, 6mmol), add them to a 100mL three-necked flask, add tert-butyl alcohol 40mL, piperidine 1mL, pump and fill with nitrogen three times, heat to 80℃ and react overnight, remove excess solvent by vacuum distillation after the raw materials are completely reacted, wash with water and extract with dichloromethane three times, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel and column chromatography, eluent is PE:DCM＝10:1 (volume ratio) to obtain about 1.5g of compound 136, yield: 50.2%. Ms: 1492.59 Preparation and characterization of OPV devices

The following is a detailed description of the preparation process of the OPV device including the above compounds through a specific device example. The OPV device structure is as follows: Indium Tin Oxide ITO/PEDOT:PSS/Active Layer/PFN-Br/Ag

The steps for preparing device 1 are as follows:

1) ITO substrate cleaning:

The ITO conductive glass anode layer was cleaned with detergent, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes, and then treated in a plasma cleaner for 5 minutes to improve surface wettability.

2) Anode buffer layer preparation

PEDOT:PSS was evenly spin-coated on ITO in air at a spin-coating speed of 3000-4000 rpm, and dried at 150° C. for 15 min to obtain an anode modification layer with a thickness of 20 nm.

3) Preparation of photoactive layer

In a glove box (inert gas atmosphere), the photoactive layer material is evenly spin-coated on the anode buffer layer at a rotation 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 4; the mass ratio of the donor material to the acceptor material is 1:1.2.

4) Preparation of cathode buffer layer

After thermal annealing on a hot plate at 100° C. for 10 minutes, the cathode buffer layer material PFN-Br was evenly spin-coated 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.

5) Cathode layer preparation

Ag was evaporated onto the cathode buffer layer in a high vacuum (1×10 ⁻⁶ mbar) to form a cathode layer with a thickness of 100 nm.

6) Packaging

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

Compound REF:

The synthetic route refers to CN 109134513A.

Device 2:

The preparation method is the same as that of device 1, except that the donor material in the active layer is compound 8.

Device 3:

The preparation method is the same as that of device 1, except that the donor material in the active layer is compound 31.

Device 4:

The preparation method is the same as that of device 1, except that the donor material in the active layer is compound 35.

Device 5:

The preparation method is the same as that of device 1, except that the donor material in the active layer is compound 54.

Device 6:

The preparation method is the same as that of device 1, except that the donor material in the active layer is compound 108.

Device 7:

The preparation method is the same as that of device 1, except that the donor material in the active layer is compound 136.

Device REF:

The preparation method is the same as that of device 1, except that the donor material in the active layer is compound REF.

The prepared organic solar cell device was tested for performance. Under the irradiation of AM1.5G standard light of a solar simulator (SS-F5-3A), the cell current-voltage curve was tested and the photoelectric conversion efficiency was calculated:

It can be seen from the device characterization of the above device embodiment that the compound protected by the present application shows a better photoelectric conversion efficiency. The reason is that the core of the compound of the present application has a larger condensed ring core than the comparative compound Ref, which is more conducive to the stacking of molecules, thereby promoting the effective transmission and collection of charges, helping the device to improve the photoelectric conversion efficiency.

The above examples further illustrate the content of the present application, but should not be construed as limiting the present application. Without departing from the spirit and substance of the present application, modifications and replacements made to the methods, steps or conditions of the present application all fall within the scope of the present application. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.

Claims (10)

1. A fused ring organic compound characterized by: the condensed ring organic compound has a structure represented by general formula (I):

wherein:

Ar ₁ 、Ar ₂ independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 30 ring atoms;

x is independently selected for each occurrence from O or C (CN) ₂ ；

Y is selected from O, S, se or NR ₉ ；

Z is independently selected from N or CR at each occurrence ₁₀ ；

R ₁ -R ₁₀ Each independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear alkylthio having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic alkylthio having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amine, -CF ₃ 、-OCF ₃ -Cl, -Br, -F, -I, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, an aryloxy group having 6 to 50 ring atoms, a heteroaryloxy group having 5 to 50 ring atoms, or a combination thereof;

wherein R is ₁ -R ₄ Wherein two adjacent groups form a ring or do not form a ring。

2. A fused ring organic compound according to claim 1, wherein: ar (Ar) ₁ 、Ar ₂ Independently selected from the group consisting of:

wherein:

* Represents a fusion site;

each occurrence of V is independently selected from N or CR ₁₁ ；

Each occurrence of W is independently selected from O, S, se, CR ₁₁ R ₁₂ Or NR ₁₂ ；

R ₁₁ -R ₁₂ Independently selected from: -H, -D, a straight chain alkyl group having 1 to 20C atoms, a straight chain alkoxy group having 1 to 20C atoms, a straight chain alkylthio group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic alkylthio group having 3 to 20C atoms, 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 combination thereof.

3. A fused ring organic compound according to claim 2, wherein: the general formula (I) is selected from the general formula (II-1), (II-2) or (II-3):

4. a fused ring organic compound according to claim 1, wherein: z is independently selected from CH or N.

5. A fused ring organic compound according to claim 1, whereinIn the following steps: in the general formula (I)

Independently selected for each occurrence from structural formula (B-1), (B-2) or (B-3):

* Represents a linking site;

preferably, R ₁ -R ₄ Each independently selected from: -H, -D, linear alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, cyano, isocyano, hydroxy, nitro, -CF ₃ -Cl, -Br, -F, -I, or combinations thereof.

6. A fused ring organic compound according to claim 1, wherein: r is ₅ -R ₈ Independently selected from H, D, or a straight chain alkyl group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or combinations thereof.

7. A fused ring organic compound according to claim 1, wherein: the fused ring organic compound is selected from the following structures:

8. a mixture, characterized by: the mixture includes the fused ring organic compound of any one of claims 1-7 and at least one organic functional material selected from an anode buffer layer material, a cathode buffer layer material, an active layer donor material, or an active layer acceptor material.

9. An electron acceptor material, characterized by: the electron acceptor material is selected from the fused ring organic compounds of any one of claims 1 to 7 or the mixtures of claim 8.

10. An organic electronic device comprising at least one functional layer, characterized in that: the functional layer material is selected from a fused ring organic compound according to any one of claims 1 to 7 or a mixture according to claim 8.