Conjugated cyclic dispiro compounds, methods of making and using the same

Abstract

The application provides a conjugated cyclic double helix compound and a preparation method and application thereof, the conjugated cyclic double helix compound has a structure as shown in formula I, rings Ar1, Ar2, a molecular fragment π, an end group Acc and a heteroaromatic ring and an oxygen-containing heptadiene can form an extended π conjugated unit system, have a larger delocalized molecular π orbital, and have multiple orthogonal structures, the introduction of the double helix structure can increase the dimension of the molecular structure and increase the channel of charge transport; in addition, the three-dimensional molecular structure can further adjust the π-π stacking between conjugated molecules, so that the molecular aggregation reaches an ideal scale, charge annihilation caused by excessive π-π stacking is avoided, and the application of the conjugated cyclic double helix compound to the construction of an organic semiconductor material with more excellent performance is helpful; in addition, the conjugated cyclic double helix compound can be applied to a solar cell as an electron acceptor, and the performance of the solar cell is improved.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor materials technology, specifically relating to a conjugate cyclic double-helical structure block, its preparation method, and its application. Background Technology

[0002] Conjugated organic semiconductor molecules have wide applications in light-emitting diodes (OLEDs), open-circuit field-effect transistors (OFETs), and open-circuit solar cells (OSCs). With the development of molecules with different configurations, one-dimensional linear polymer molecules, two-dimensional planar molecules, and three-dimensional molecules exhibit unique photoelectric properties. Three-dimensional conjugated spiromolecules, represented by 9,9-spirofluorene, possess a unique orthogonal structure and are used in OLEDs, perovskite hole-filling materials, and non-fullerene small molecule acceptor materials. The differences between various conjugated organic semiconductor molecules mainly lie in the random combination and transformation of core units, bridging agents, and terminal units. The selection and combination of these three elements endow conjugated organic semiconductor materials with different properties. For example, replacing the benzene ring unit (as a bridging agent) in the 9,9-spirofluorene molecule with a thiophene unit can lower the molecular energy level and band gap, change the molecular stacking pattern, and increase the charge mobility. Because the α-site of thiophene is highly reactive, it can undergo various electrophilic and nucleophilic reactions, thereby connecting more types of bridging agents and terminal units, broadening the molecular dimension.

[0003] Currently, the helical structures of conjugated organic semiconductor molecular materials reported in the literature are mostly single orthogonal structures, and are mostly linear polymers or small organic molecules. Due to the strong intermolecular interactions, these materials have poor solubility in solvents, and the solubility of cyano-substituted molecules is even more difficult. At the same time, there are fewer charge transport channels. Therefore, structural design of conjugated organic semiconductor molecules to improve their solubility in solvents and increase charge transport channels is a key issue.

[0004] CN109575241A discloses a conjugated polymer based on quinone compounds. This organic conjugated polymer has a wide molecular weight distribution, meaning that the material contains combinations of compounds formed by different numbers of repeating units. Due to the wide molecular weight distribution, the material is difficult to purify and has poor reproducibility. CN102224157A discloses an organic semiconductor material with a two-dimensional planar structure. This material has limited charge transport channels and poor charge transport performance.

[0005] Therefore, developing a conjugated organic compound with a single molecular weight distribution, improving its solubility in solvents, and increasing charge transport channels is a key issue. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a conjugated cyclic double-spiral compound, its preparation method, and its applications. By designing the structure of the conjugated cyclic double-spiral compound, the dimensionality of the molecular structure is increased, and the channels for charge transport are expanded. Furthermore, the three-dimensional molecular structure can further regulate the π-π stacking between conjugated molecules, enabling molecular aggregation to reach an ideal scale.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a conjugated cyclic double-spiral compound having the structure shown in Formula I:

[0009]

[0010] Among them, ring Ar1 and ring Ar2 are each independently selected from any one of substituted or unsubstituted C6-C30 aromatic rings and substituted or unsubstituted C4-C30 heteroaromatic rings.

[0011] X1 and X2 are each independently selected from any one of O, S, or Se.

[0012] R 11 R 12 Each is independently selected from any one of C6-C12 straight-chain or branched alkyl groups.

[0013] π is selected from any one of substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C4-C30 heteroarylene.

[0014] Acc is selected from any one of the following groups:

[0015]

[0016] in, The linking site of the representative group.

[0017] R 13 R 14 R 15 Each is independently selected from any one of C6-C12 straight-chain or branched alkyl groups.

[0018] U1 and U2 are each independently selected from either hydrogen or halogen.

[0019] The substituents in ring Ar1 and ring Ar2 are each independently selected from any one of C6-C12 straight-chain or branched alkyl groups.

[0020] The substituents in π are selected from any one of halogen, C6-C12 linear or branched alkyl, and -COOR, and R is selected from any one of C6-C12 linear or branched alkyl.

[0021] For the conjugated cyclic bis-spiro structure compound provided by the present invention, ring Ar1, ring Ar2, molecular fragment π, end group Acc and heteroaryl-fused oxepin can form a more extended π-conjugated unit system, have a larger delocalized molecular π orbital, and have multiple orthogonal structures. The introduction of the bis-spiro structure can increase the dimension of the molecular structure and increase the channels for charge transport. In addition, the three-dimensional molecular structure can further regulate the π-π stacking between conjugated molecules, enabling the molecular aggregation to reach an ideal scale and avoiding charge annihilation caused by excessive π-π stacking.

[0022] In the present invention, each of C6-C30 can independently be C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28 or C30, etc.

[0023] Each of C4-C30 can independently be C4, C5, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28 or C30, etc.

[0024] Each of C6-C12 can independently be C6, C7, C8, C9, C10, C11 or C12, etc.

[0025] Halogen in the present invention includes F or Cl.

[0026] In the present invention, for the description of chemical elements, if there is no special explanation, the concept of isotopes with the same chemical properties is included. For example, hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H (tritium, T), or any combination of at least two of them; carbon (C) includes 12 C, 13 C, etc. In the present invention, taking methyl as an example, it can be represented as -CH3, -CD3, etc.

[0027] The C6-C30 (such as C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28 or C30, etc.) aromatic rings are further preferably C6-C10 aromatic rings, and exemplary include but are not limited to: benzene ring, biphenyl ring, terphenyl ring, naphthalene ring, anthracene ring, phenanthrene ring, indene ring or fluorene ring, etc.

[0028] The C4-C30 (C4, C5, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28 or C30, etc.) heteroaromatic ring, wherein the heteroatoms include O, N or S, etc., and more preferably C4-C10 heteroaromatic ring, which includes, but is not limited to: furan ring, thiophene ring, pyridine ring, pyrazine ring, and dithiophene ring pyrrole ring, etc.

[0029] The C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12, etc.) straight-chain or branched alkyl groups, exemplary including but not limited to: n-hexyl, neohexyl, n-octyl, isooctyl, n-heptyl, isoheptyl, n-nonyl, n-decyl, or dimethylpentyl, etc.

[0030] The C6-C30 (e.g., C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, or C30, etc.) arylene groups, more preferably C6-C10 arylene groups, exemplarily including but not limited to phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrene, indene, fluorene, fluorenyl, triphenylene, pyrene, perylene, etc. Or phenylene oxide, etc.

[0031] The C4-C30 (C4, C5, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, or C30, etc.) heteroaryl groups, wherein the heteroatoms include O, N, or S, etc., are further preferred. C4-C10 heteroaryl groups are included, but are not limited to, thiopheneyl, pyrrolyl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phenanthrolineyl, imidazolyl, thiazolyl, oxazolyl, benzimidazolyl, benzothiazolyl, benzoxoxazolyl, benzofuranyl, or benzothiopheneyl, etc.

[0032] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents (at least two), the multiple (at least two) substituents can be the same or different groups. The substituents can be attached to any position within the group. The same expressions used below have the same meaning.

[0033] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0034] As a preferred technical solution, the ring Ar1 and ring Ar2 are each independently selected from any one of substituted or unsubstituted C6-C10 aromatic rings and substituted or unsubstituted C4-C10 heteroaromatic rings; wherein, the substituents in the ring Ar1 and ring Ar2 are each independently selected from any one of C6-C12 straight-chain or branched alkyl groups.

[0035] Each of C6 to C10 can independently be C6, C7, C8, C9, or C10, etc.

[0036] Each of C4 to C10 can independently be C4, C5, C6, C7, C8, C9, or C10, etc.

[0037] As a preferred technical solution, the ring Ar1 and ring Ar2 are each independently selected from any one of the following groups:

[0038]

[0039] In this context, the dashed lines represent the fused bonds of the rings; Y is selected from C or Si; R 21 R 22 R 23 Each is independently selected from any one of C6-C12 straight-chain or branched alkyl groups.

[0040] As a preferred technical solution, the π is selected from any one of substituted or unsubstituted C6-C10 arylene groups and substituted or unsubstituted C4-C10 heteroarylene groups; wherein, the substituent in the π is selected from any one of halogens, C6-C12 straight-chain or branched alkyl groups, and -COOR; R is selected from any one of C6-C12 straight-chain or branched alkyl groups.

[0041] As a preferred technical solution, the π group is selected from any one of the following groups:

[0042]

[0043] in, Represents the linkage site of the group; R 31 R 32 R 33 R 34 R 35 R 36 R 37 R 38 R 39 Each is independently selected from any one of C6-C12 straight-chain or branched alkyl groups; W1 and W2 are each independently selected from any one of hydrogen or halogen; Z is selected from C or Si.

[0044] n1 is an integer selected from 1 to 4, for example, it can be 1, 2, 3 or 4.

[0045] As a preferred technical solution, the conjugated cyclic double-spiral compound includes any one of 1 to 5:

[0046]

[0047]

[0048]

[0049] In a second aspect, the present invention provides a method for preparing a conjugated cyclic double-spiral compound as described in the first aspect, the method comprising the following steps:

[0050] (1) The compound shown in formula II reacts with the compound shown in formula III to obtain the compound shown in formula IV, as shown in the following reaction formula:

[0051]

[0052] (2) The compound of formula IV obtained in step (1) reacts with trimethylchlorosilane to obtain the compound of formula V, and the reaction formula is as follows:

[0053]

[0054] In formula V, TMS represents trimethylsilyl.

[0055] (3) The compound of formula V obtained in step (2) reacts with the compound of formula VI to obtain the compound of formula VII. The reaction formula is as follows:

[0056]

[0057] Among them, R 41 R 42 The same and selected from either halogen or trimethylsilyl.

[0058] (4) The compound of formula VII obtained in step (3) undergoes a bromination reaction to obtain the compound of formula VIII, as shown in the following reaction formula:

[0059]

[0060] (5) The compound of formula VIII obtained in step (4) undergoes a condensation reaction to obtain the compound of formula IX, as shown in the following reaction formula:

[0061]

[0062] (6) The compound of formula IX obtained in step (5) reacts with π-Bpin and then undergoes an aldehyde reaction, or the compound of formula IX reacts with CHO-π-Bpin to obtain the compound of formula X, as shown in the following reaction formula:

[0063]

[0064] The structural formula of the π-Bpin is as follows: The CHO-π-Bpin structure is as follows:

[0065] The aldehyde group connected to π in Formula X of this invention can be introduced through the aldehyde alkylation reaction or through the aldehyde group inherent in the CHO-π-Bpin.

[0066] (7) The compound of formula X obtained in step (6) reacts with the electron-accepting unit to obtain the conjugated cyclic double-spiral compound of formula I, as shown in the following reaction formula:

[0067]

[0068] Preferably, the reaction temperature in step (1) is -78-25℃, for example, it can be -78℃, -70℃, -60℃, -50℃, -40℃, -30℃, -20℃, -10℃, 0℃, 10℃, 15℃, 20℃ or 25℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0069] Preferably, the reaction time in step (1) is 1-24h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0070] Preferably, the reaction in step (1) is carried out in a solvent.

[0071] Preferably, the solvent in step (1) comprises a combination of diisopropylamine, n-butyllithium and copper chloride.

[0072] Preferably, the reaction temperature in step (2) is -78-25℃, for example, it can be -78℃, -70℃, -60℃, -50℃, -40℃, -30℃, -20℃, -10℃, 0℃, 10℃, 15℃, 20℃ or 25℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0073] Preferably, the reaction time in step (2) is 20-36 hours, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, or 36 hours, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0074] Preferably, the reaction in step (2) is carried out in a solvent.

[0075] Preferably, the solvent in step (2) includes n-butyllithium.

[0076] Preferably, the reaction temperature in step (3) is -78-25℃, for example, it can be -78℃, -70℃, -60℃, -50℃, -40℃, -30℃, -20℃, -10℃, 0℃, 10℃, 15℃, 20℃ or 25℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0077] Preferably, the reaction time in step (3) is 20-36 hours, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, or 36 hours, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0078] Preferably, the reaction in step (3) is carried out in a solvent.

[0079] Preferably, the solvent in step (3) comprises a combination of n-butyllithium and tetrahydrofuran.

[0080] Preferably, the temperature of the bromination reaction in step (4) is -25 to 25°C, for example, it can be -25°C, -20°C, -10°C, 0°C, 10°C, 15°C, 20°C or 25°C, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0081] Preferably, the bromination reaction time in step (4) is 20-36 hours, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, or 36 hours, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0082] Preferably, the bromination reaction in step (4) is carried out in a solvent.

[0083] Preferably, the solvent in step (4) comprises a combination of chloroform and N,N-dimethylformamide.

[0084] Preferably, the brominating agent used in step (4) includes N-bromosuccinimide.

[0085] Preferably, the temperature of the condensation reaction in step (5) is 0-25°C, for example, it can be 0°C, 5°C, 10°C, 15°C, 20°C or 25°C, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0086] Preferably, the condensation reaction time in step (5) is 20-36 hours, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, or 36 hours, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0087] Preferably, the condensation reaction in step (5) is carried out in a solvent.

[0088] Preferably, the solvent in step (5) comprises a combination of dichloromethane and boron trifluoride-diethyl ether.

[0089] Preferably, when the compound shown in formula IX in step (6) reacts with π-Bpin or CHO-π-Bpin, the reaction temperature is 25-100℃, for example, 25℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃ or 100℃, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0090] Preferably, when the compound shown in formula IX in step (6) reacts with π-Bpin or CHO-π-Bpin, the reaction time is 18-72h, for example, it can be 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 40h, 50h, 60h, 70h or 72h, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0091] Preferably, the reaction of the compound shown in formula IX in step (6) with π-Bpin or CHO-π-Bpin is carried out in the first solvent;

[0092] Preferably, in step (6), the first solvent comprises a combination of tri-tert-butylphosphine tetrafluoroborate and potassium carbonate solution;

[0093] Preferably, the reaction of the compound shown in formula IX in step (6) with π-Bpin or CHO-π-Bpin is carried out in the presence of a catalyst.

[0094] Preferably, the catalyst in step (6) comprises tetra(triphenylphosphine)palladium.

[0095] Preferably, the reaction product of the compound shown in formula IX in step (6) with π-Bpin is the compound shown in formula XI:

[0096]

[0097] Preferably, after the reaction of the compound shown in formula IX with π-Bpin in step (6) is completed, the aldehyde reaction of the compound shown in formula XI with phosphorus oxychloride and N,N-dimethylformamide is further performed.

[0098] Preferably, the temperature of the aldehyde oxidization reaction is -10 to 100°C, for example, it can be -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0099] Preferably, the aldehyde oxidization reaction time is 8-24 hours, for example, it can be 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0100] Preferably, the aldehyde reaction is carried out in a second solvent.

[0101] Preferably, the second solvent comprises dichloroethane.

[0102] Preferably, the reaction temperature in step (7) is 50-90°C, for example, it can be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0103] Preferably, the reaction time in step (7) is 18-24h, for example, it can be 18h, 19h, 20h, 21h, 22h, 23h or 24h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0104] Preferably, the reaction in step (7) is carried out in a solvent.

[0105] Preferably, the solvent in step (7) comprises a combination of chloroform and pyridine.

[0106] Thirdly, the present invention provides an organic semiconductor material, which is constructed from a conjugated cyclic double-spiral compound as described in the first aspect.

[0107] Fourthly, the present invention provides a solar cell comprising a conjugated cyclic double-spiral compound as described in the first aspect and / or an organic semiconductor material as described in the third aspect.

[0108] Compared with the prior art, the present invention has the following beneficial effects:

[0109] The conjugated cyclic double-spiral compound provided by this invention can form a more extended π-conjugated unit system with cyclic Ar1, cyclic Ar2, molecular segment π, terminal group Acc, and heteroaromatic cyclohepta-heptadiene, which has a larger delocalized molecular π orbital. This helps to construct organic semiconductor materials with better performance. In addition, it can also be used as an electron acceptor in solar cells to improve the performance of solar cells. Attached Figure Description

[0110] Figure 1 These are the liquid UV-Vis absorption spectra of compound 1 and compound 3, which have conjugated cyclic double-spiral structures.

[0111] Figure 2 These are the UV-Vis absorption spectra of thin films of compounds 1 and 3 with conjugated cyclic double-spiral structures. Detailed Implementation

[0112] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof.

[0113] The sources of some components in the following examples and comparative examples are as follows:

[0114] When both ring Ar1 and ring Ar2 are benzene rings, the compound shown in formula VI can be prepared according to the reference Org. Lett. 2013, 15, 4642. All other raw materials are commercially available, and some components are sourced as follows:

[0115] (1) PM6: Suzhou Nakai Technology Co., Ltd., 1802013-83-7, number average molecular weight is 20000-60000;

[0116] (2) H1: Prepared according to reference J.Org.Chem 2022875057;

[0117] (3) H2: Refer to the following reaction route:

[0118]

[0119] The following are exemplary examples of the preparation of the conjugated cyclic double-spiral compound of the present invention.

[0120] Example 1

[0121] A conjugated cyclic double-spiral compound 1 has the following structure:

[0122]

[0123] A method for preparing a conjugated cyclic double-spiral compound 1, the method comprising the following steps:

[0124]

[0125] Diisopropylamine (13 mL, 92.55 mmol) was added to a 250 mL dry three-necked round-bottom flask and dissolved in 100 mL dry tetrahydrofuran. The solution was cooled to -78 °C, and under argon protection, 30 mL of a 2.5 M, 74.04 mmol solution of n-butyllithium in n-hexane was added dropwise. After stirring for 20 min, 30 mL of a tetrahydrofuran solution of compound ① (20 g, 61.7 mmol) was added dropwise. The mixture was stirred at low temperature for 1 h, and then anhydrous copper chloride powder (8.3 g, 61.7 mmol) was rapidly added, producing a deep blue solution. This solution was slowly heated to room temperature and stirred continuously for 20 h. It was then diluted with 50 mL of n-hexane and filtered through a silica gel column. The filtrate was evaporated to dryness to give a pale yellow oily liquid, compound ② (19.6 g, yield: 91%).

[0126] 1 H-NMR (400MHz, CDCl3): δ2.66 (t, J=8Hz, 4H), 1.45-1.32 (m, 14H), 0.92-0.84 (m, 8H).

[0127] 13C-NMR (100MHz, CDCl3): 141.5, 128.6, 114.6, 111.1, 31.6, 30.4, 29.1, 28.6, 22.6, 14.1.

[0128]

[0129] Compound ② (18.55 g, 28.5 mmol) was added to a 250 mL dry three-necked round-bottom flask and dissolved in 50 mL dry tetrahydrofuran. The mixture was cooled to -78 °C, and 22.8 mL of a hexane solution of n-butyllithium (2.5 M, 57.1 mmol) was added dropwise under argon protection. After stirring for 30 min, a tetrahydrofuran solution of trimethylchlorosilane (7.6 mL, 59.9 mmol) was added. The mixture was then slowly heated to room temperature and stirred continuously for 20 h. The reaction was quenched by adding 50 mL of saturated ammonium chloride solution and extracted with 200 mL of dichloromethane. The organic phase was washed with brine and dried and concentrated with magnesium sulfate to obtain a brown oily substance. After elution with n-hexane by column chromatography, a pale yellow oily liquid, namely compound ③ (16.55 g, yield: 91.1%), was obtained.

[0130] 1 H-NMR (400MHz, CDCl3): δ2.68 (t, J=8Hz, 4H), 1.43-1.34 (m, 14H), 0.93-0.89 (m, 8H), 0.36-0.33 (m, 18H).

[0131]

[0132] Compound ③ (7 g, 10.99 mmol) was dissolved in 10 mL of dry tetrahydrofuran solution in a 250 mL dry three-necked round-bottom flask and cooled to -78 °C. Under argon protection, 9 mL of a hexane solution of n-butyllithium (2.5 M, 22.01 mmol) was added dropwise, and the mixture was stirred at low temperature for 25 min. Then, 30 mL of a tetrahydrofuran solution of compound ④ (5.5 g, 16.48 mmol) was added dropwise. The resulting orange solution was slowly heated to room temperature and stirred continuously for 20 h, followed by quenching the reaction with 10 mL of saturated ammonium chloride solution. The organic phase was extracted and separated with 50 mL of dichloromethane, dried over magnesium sulfate, and the resulting orange-red oil was eluted by column chromatography with a 15% dichloromethane / n-hexane mixture to give a pale yellow solid, compound ⑤ (7.1 g, yield: 61%).

[0133] 1H-NMR (400MHz, CDCl3): δ7.40 (s, 2H), 6.87 (s, 2H), 4.36 (s, 2H), 2.02 (t, J=8Hz, 2 H), 1.43-1.30 (m, 9H), 1.26-1.15 (m, 5H), 0.95-0.80 (m, 15H), 0.32-0.25 (m, 62H).

[0134] 13 C-NMR (100MHz, CDCl3): δ159.4, 157.3, 149.0, 143.4, 143.0, 142.8, 142.5, 1 39.8, 138.8, 135.0, 129.5, 128.7, 79.5, 32.1, 32.0, 30.5, 30.2, 22.6, 14.1.

[0135]

[0136] Compound ⑥ (6.5 g, 5.64 mmol) was dissolved in 50 mL of dry chloroform solution and 10 mL of dry N,N-dimethylformamide solution in a 50 mL dry three-necked round-bottom flask and cooled to -25 °C. Under argon protection, 10 mL of N,N-dimethylformamide solution containing N-bromosuccinimide (6.52 g, 36.7 mmol) was added dropwise. The resulting mixture was slowly heated to room temperature and stirred continuously in the dark for 20 h. After dilution with 50 mL of dichloromethane and separation with water, the organic phase was dried over magnesium sulfate. Evaporation to dryness yielded a brown oily substance, which was eluted by column chromatography with a 25% dichloromethane / n-hexane mixture to give a light brown solid, compound ⑥ (4.7 g, yield: 69%).

[0137] 1 H-NMR (400MHz, CDCl3): δ7.04 (s, 2H), 6.83 (s, 2H), 3.60 (s, 2H), 2.01 (t, J=8Hz, 2H), 1.70 (t, J=8Hz, 2H), 1.25-0.80 (m, 30H).

[0138] 13 C-NMR (100MHz, CDCl3): 154.3, 152.6, 140.1, 137.8, 135.3, 133.6, 125.2, 125.0, 80.35, 31.7, 30.2, 29.3, 28.7, 22.6, 14.2.

[0139]

[0140] Compound ⑥ (4 g, 3.35 mmol) was dissolved in 200 mL of dry dichloromethane solution in a 500 mL dry three-necked round-bottom flask. Under argon protection, 20 mL of a dichloromethane solution of boron trifluoride-diethyl ether (2.38 g, 16.8 mmol) was added dropwise. The resulting dark green solution was stirred continuously at room temperature for 20 h. The reaction was quenched with 50 mL of saturated sodium bicarbonate solution. After separation of the organic phase, the solution was dried over magnesium sulfate. Evaporation yielded a brown solid, which was eluted by column chromatography with a 25% dichloromethane / n-hexane mixture to obtain a light brown solid, compound ⑦ (1.9 g, yield: 50%).

[0141] 1 H-NMR (400MHz, CDCl3): δ6.34 (s, 4H), 1.87 (t, J = 8Hz, 4H), 1.19-1.15 (m, 5H), 1.06-1.02 (m, 5H), 0.85-0.79 (m, 16H).

[0142] 13 C-NMR (100MHz, CDCl3): δ150.9, 141.1, 138.6, 137.6, 135.1, 112.4, 111.0, 84.9, 31.7, 29.7, 29.5, 28.8, 22.6, 14.1.

[0143]

[0144] Compound ⑦ (1.5 g, 1.3 mmol), tri-tert-butylphosphine tetrafluoroborate (45 mg, 0.156 mmol), and 2-(3-hexylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane (4.6 g, 15.6 mmol) were added to a 100 mL dry three-necked round-bottom flask and dissolved in 30 mL tetrahydrofuran. 20 mL of potassium carbonate solution (2 M) was then added. After bubbling with argon for 20 min, tetra(triphenylphosphine)palladium catalyst (93 mg, 0.08 mmol) was rapidly added. The mixture was then bubbled with argon again for 10 min, and the solution was refluxed at 70 °C and stirred for 48 h to obtain a dark-colored solution. After cooling, the solution was extracted with 50 mL of dichloromethane. After separation of the organic phase, it was dried with magnesium sulfate and evaporated to dryness to obtain a brown oily substance. After elution by column chromatography with a mixed solvent of 50% dichloromethane / n-hexane, an orange solid, namely compound ⑧ (1.5 g, yield: 68%), was obtained.

[0145] 1H-NMR (400MHz, CDCl3): δ7.55 (d, J=8Hz, 4H), 7.48 (d, J=8Hz, 2H), 6.92 (d, J=8Hz, 4H), 6.87 (d, J=8Hz, 2H), 2.75 ( t, J=8Hz, 8H), 2.63 (t, J=8Hz, 4H), 1.98-1.77 (m, 8H), 1.70-1.56 (m, 4H), 1.50-1.20 (m, 24H), 1.20-0.84 (m, 12H).

[0146] 13 C-NMR (100MHz, CDCl3): δ153.8, 144.6, 143.1, 142.4, 140.8, 140.3, 139.0, 138.8, 138.0, 137.1, 128.7, 12 4.2, 84.7, 53.5, 31.6, 31.4, 31.1, 30.4, 30.1, 29.8, 29.7, 29.2, 28.9, 28.1, 22.6, 22.5, 22.4, 14.1, 13.9.

[0147] Under argon atmosphere, phosphorus oxychloride (0.7 mL) was added to a 1,2-dichloroethane solution (50 mL) of compound ⑧ (1.1 g, 0.65 mmol) and N,N-dimethylformamide (DMF, 0.7 mL). The resulting mixture was stirred and refluxed for 12 hours, then cooled to 0 °C. A saturated sodium acetate solution (40 mL) was slowly added to the resulting mixture, and the mixture was stirred at room temperature for 2 hours. The resulting mixture was extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate. After removing the solvent, the crude product was purified by silica gel column chromatography, eluting with a 50% dichloromethane / n-hexane mixture to give an orange solid, compound ⑨ (970 mg, 80%).

[0148] 1 H-NMR (400MHz, CDCl3): δ9.86 (s, 2H), 9.79 (s, 4H), 7.65 (s, 2H), 7.55 (s, 4H), 6.77 (s, 4H), 2.77 (t, J=8Hz , 8H), 2.61 (t, J=8Hz, 4H), 1.98-1.87 (m, 4H), 1.70-1.58 (m, 15H), 1.50-1.20 (m, 41H), 1.20-0.64 (m, 41H).

[0149] 13C-NMR: δ182.8, 182.2, 153.8, 144.6, 143.1, 142.4, 140.8, 140.3, 139.0, 138.8, 138.0, 137.1, 128.7, 124 .2, 84.7, 53.5, 31.6, 31.4, 31.1, 30.4, 30.1, 29.8, 29.7, 29.2, 28.9, 28.1, 22.6, 22.5, 22.4, 14.1, 13.9.

[0150]

[0151] Compound ⑨ (500 mg, 0.27 mmol) and 3-ethylene(1-dicyano)-1-(5,6-difluoro)indanone (496 mg, 2.16 mmol) were added to a dry three-necked round-bottom flask and dissolved in 20 mL of chloroform. The mixture was heated to 50 °C under argon protection and stirred before adding 0.1 mL of pyridine. The resulting dark solution was refluxed and stirred for 20 h and then cooled. After evaporating the solvent to dryness, a dark blue solid was obtained. This solid was eluted by column chromatography with a 50% dichloromethane / n-hexane mixture to obtain the dark blue solid, compound 1 (700 mg, yield: 83%).

[0152] 1 H-NMR (400MHz, CDCl3): δ8.72 (s, 6H), 8.57-8.49 (m, 6H), 7.68 (s, 2H), 7.66 (s, 4H), 7.57 (s, 6H), 7.05 (s, 4H), 2, 82 (t, J=8Hz, 8H), 2.69 (t, J=8Hz , 4H), 2.10 (s, 4H), 1.69-1.64 (m, 10H), 1.60 (bs, 20H), 1.35 (bs, 12H), 1 .25(bs, 22H), 1.00-0.96(m, 6H), 0.83-0.77(m, 28H), 0.67-0.51(m, 8H).

[0153] 13 C-NMR (100MHz, CDCl3): δ185.7, 153.3, 149.1, 148.3, 146.2, 144.7, 144.1, 142.1, 139.7, 137.5, 137.1, 136.6, 136 .5, 134.5, 134.3, 129.6, 125.3, 122.7, 121.7, 114.9, 113.9, 31.6, 31.5, 30.5, 29.9, 29.1, 28.8, 22.6, 22.5, 14.1.

[0154] Example 2

[0155] A conjugated cyclic double-spiral compound 2 has the following structure:

[0156]

[0157] A method for preparing a conjugated cyclic double-spiral compound 2, which differs from Example 1 only in that the equimolar amount of 3-ethylene(1-dicyano)1-(5,6-difluoro)indanone in step (7) is replaced with 3-ethylene(1-dicyano)1-indanone. The other raw materials, process parameters and steps are the same as in Example 1, and compound 2 (590 mg, yield: 75%) is prepared.

[0158] 1 H-NMR (400MHz, CDCl3): δ8.72 (s, 4H), 8.69 (s, 2H), 8.62-8.58 (m, 6H), 7.79-7.68 (m, 18H), 7.63 (s, 6H), 7.03 (s, 4H), 2.83 (t, J=8Hz, 8H), 2.71 (t , J=8Hz, 4H), 2.18(bs, 4H), 1.69(bs, 14H), 1.53(s, 28H), 1.37(s, 14H), 1.25 (s, 14H), 0.99-0.97 (m, 6H), 0.84-0.79 (m, 30H), 0.66-0.62 (m, 8H).

[0159] 13 C-NMR (100MHz, CDCl3): δ187.9, 160.1, 148.5, 147.8, 142.3, 141.9, 141.0, 139.9, 137.9, 137.5, 137.4, 137.1, 135.8, 135.2, 134. 7, 134.5, 125.5, 125.2, 123.6, 122.5, 114.5, 114.2, 69.3, 31.7, 31.6, 31.5, 30.6, 29.9, 29.7, 29.4, 29.1, 22.6, 22.5, 14.1, 14.0.

[0160] Example 3

[0161] A conjugated cyclic double-spiral compound 3 has the following structure:

[0162]

[0163] A method for preparing a conjugated cyclic double-spiral compound 3, steps (1) and (2) are the same as in Example 1, and the remaining experimental steps are as follows:

[0164]

[0165] Compound ③ (0.7 g, 1 mmol) was dissolved in 5 mL of dry tetrahydrofuran solution in a 250 mL dry three-necked round-bottom flask and cooled to -78 °C. Under argon protection, 0.9 mL of a hexane solution of n-butyllithium (2.5 M, 2.2 mmol) was added dropwise, and the mixture was stirred at low temperature for 25 min. Then, 3 mL of a tetrahydrofuran solution of compound ⑩ (2,7-dibromo-9-fluorenone) (0.67 g, 2 mmol) was added dropwise. The resulting orange solution was slowly heated to room temperature and stirred continuously for 20 h, followed by quenching the reaction with 10 mL of saturated ammonium chloride solution. The organic phase was extracted and separated with 20 mL of dichloromethane, dried over magnesium sulfate, and then evaporated to dryness to obtain an orange-red oil. This oil was eluted by column chromatography with a 15% dichloromethane / n-hexane mixed solvent to obtain a pale yellow solid, which is the compound. (0.6g, yield: 52%).

[0166] 1 H-NMR (400MHz, CDCl3): δ7.80 (d, J=8Hz, 4H), 7.72 (s, 4H), 7.63 (d, J=8Hz, 4H); 4.32 (s, 2H), 2.5 2(t, J=8Hz, 4H), 1.50-1.43(m, 4H), 1.30-1.15(m, 12H), 0.98-0.85(m, 6H), 0.35-0.26(m, 18H).

[0167] 13 C-NMR (100MHz, CDCl3): δ157.3, 145.4, 143.0, 141.4, 140.0, 138.8, 135.5, 134.8, 127.8, 78.5, 32.1, 32.0, 30.5, 30.2, 22.6, 14.1, 7.5.

[0168]

[0169] Add the compound to a 50 mL dry three-necked round-bottom flask. (0.5 g, 0.4 mmol) was dissolved in 10 mL of dry chloroform solution and 2 mL of dry N,N-dimethylformamide solution and cooled to -25 °C. Under argon protection, 10 mL of N,N-dimethylformamide solution containing 0.2 g of N-bromosuccinimide (N,N-dimethylformamide) was added dropwise. The resulting mixture was slowly heated to room temperature and stirred continuously in the dark for 20 h. After dilution with 10 mL of dichloromethane and separation with water, the organic phase was dried over magnesium sulfate. Evaporation to dryness yielded a brown oily substance, which was eluted by column chromatography with a 25% dichloromethane / n-hexane mixture to obtain a light brown solid, the compound. (0.4g, yield: 86%).

[0170] 1 H-NMR (400MHz, CDCl3): δ7.84 (d, J=8Hz, 4H), 7.72 (s, 4H), 7.53 (d, J=8Hz, 4H), 3.80 (s, 2 H), 2.71 (t, J=8Hz, 4H), 1.70-1.62 (m, J=8Hz, 4H), 1.35-1.20 (m, 12H), 0.9 (t, J=8Hz, 6H).

[0171] 13 C-NMR (100MHz, CDCl3): 153.3, 144.6, 141.1, 140.8, 139.8, 134.3, 131.6, 130.2, 123.0, 111.3, 80.35, 32.7, 31.2, 29.5, 28.2, 22.6, 14.2.

[0172]

[0173] Add the compound to a 100 mL dry three-necked round-bottom flask. (0.4 g, 0.34 mmol) was dissolved in 20 mL of dry dichloromethane solution. Under argon protection, 2 mL of a dichloromethane solution containing boron trifluoride-diethyl ether (0.24 g, 1.7 mmol) was added dropwise. The resulting dark green solution was stirred continuously at room temperature for 20 h. The reaction was quenched with 10 mL of saturated sodium bicarbonate solution. After separation of the organic phase, the solution was dried over magnesium sulfate. Evaporation to dryness yielded a brown solid, which was eluted by column chromatography with a 25% dichloromethane / n-hexane mixture to give a light brown solid (0.2 g, yield: 50%).

[0174] 1 H-NMR (400MHz, CDCl3): δ7.85 (d, J=8Hz, 4H), 7.72 (s, 4H), 7.50 (d, J=8Hz, 4H), 2.25 (t, J=8Hz, 4H), 1.19-1.15 (m, 4H), 1.12-1.06 (m, 12H), 0.88-0.80 (m, 6H).

[0175] 13 C-NMR (100MHz, CDCl3): δ152.9, 145.1, 142.6, 141.6, 139.1, 136.3, 131.4, 130.6, 124.3, 111.0, 90.9, 31.9, 30.7, 29.5, 28.8, 22.6, 14.1.

[0176] (6)-(7) can be referred to steps (6) and (7) of Example 2 to prepare compound 3.

[0177] 1 H-NMR (400MHz, CDCl3): δ8.82 (s, 4H), 8.79 (s, 2H), 8.71-8.67 (m, 6H), 7.87- 7.82(m, 8H), 7.79-7.73(m, 18H), 7.72-7.60(m, 6H), 7.57-7.50(m, 4H), 2.83( t, J=8Hz, 8H), 2.71 (t, J=8Hz, 4H), 2.25 (t, J=8Hz, 4H), 1.65-1.60 (m, 16H), 1. 30-1.27 (m, 8H), 1.12-1.06 (m, 16H), 0.88-0.80 (m, 36H), 0.75-0.72 (m, 12H).

[0178] 13 C-NMR (100MHz, CDCl3): δ185.9, 158.4, 156.9, 155.5, 152.9, 147.3, 145.1, 142.6, 141.6, 141.3, 139.9, 139.7, 139.1, 138.1, 136.3, 135. 2, 134.6, 133.4, 131.4, 130.6, 124.3, 123.5, 122.8, 114.4, 111.0, 69 .9, 31.9, 31.5, 30.8, 30.7, 29.5, 29.3, 28.8, 28.7, 22.6, 22.5, 14.1.

[0179] Example 4

[0180] A conjugated cyclic double-spiral compound 1 has the following structure:

[0181]

[0182] A method for preparing a conjugated cyclic double-spiral compound 1 differs from Example 1 only in step (6). All other raw materials, process parameters, and steps are the same as in Example 1. Step (6) is as follows:

[0183]

[0184] Compound ⑦ (1.73 g, 1.47 mmol), tri-tert-butylphosphine tetrafluoroborate (51.2 mg, 0.176 mmol), and 2-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)-3-hexylthiophene-5-aldehyde (6 g, 18.6 mmol) were added to a 100 mL dry three-necked round-bottom flask and dissolved in 30 mL tetrahydrofuran. 20 mL of potassium carbonate solution (2 M) was then added. After bubbling with argon for 20 min, tetra(triphenylphosphine)palladium catalyst (60 mg, 0.09 mmol) was rapidly added. The mixture was then bubbled with argon again for 10 min, and the solution was refluxed at 70 °C and stirred for 48 h to obtain a dark-colored solution. After cooling, the solution was extracted with 50 mL of dichloromethane. After separation of the organic phase, it was dried with magnesium sulfate and evaporated to dryness to obtain a brown oily substance. After elution by column chromatography with a mixed solvent of 50% dichloromethane / n-hexane, an orange solid, namely compound ⑨ (2.06 g, yield: 75%), was obtained.

[0185] 1 H-NMR (400MHz, CDCl3): δ7.57 (d, J=8Hz, 4H), 7.47 (d, J=8Hz, 2H), 6.92 (d, J=8Hz, 4H), 6.87 (d, J=8Hz, 2H), 2.76 ( t, J=8Hz, 8H), 2.66 (t, J=8Hz, 4H), 1.98-1.79 (m, 8H), 1.70-1.58 (m, 4H), 1.53-1.20 (m, 24H), 1.20-0.84 (m, 12H).

[0186] 13 C-NMR (100MHz, CDCl3): δ154.1, 144.5, 143.1, 142.4, 140.8, 140.3, 139.1, 138.7, 138.0, 137.1, 128.5, 12 4.3, 84.7, 53.8, 31.6, 31.2, 31.1, 30.5, 30.1, 29.8, 29.6, 29.2, 28.9, 28.4, 22.8, 22.5, 22.2, 14.1, 14.0.

[0187] Material characterization and performance testing:

[0188] (1) Liquid UV-Vis Absorption Spectroscopy: The conjugated cyclic double-spiral compound provided in Examples 1 and 3 was dissolved in chloroform solution, and UV-Vis absorption spectroscopy was performed (testing instrument: PerkinElmer Lambda 750 spectrophotometer). The test results are as follows: Figure 1 The liquid UV-Vis absorption spectra of conjugated cyclic double-spiral compound 1 and conjugated cyclic double-spiral compound 3 are shown.

[0189] (2) UV-Vis absorption spectrum of thin film: The conjugated cyclic double-spiral compound provided in Examples 1 and 3 was prepared into a thin film by spin-coating on quartz glass, and the UV-Vis absorption spectrum was tested. The test results are as follows: Figure 2 The UV-Vis absorption spectra of thin films of conjugated cyclic double-spiral compound 1 and conjugated cyclic double-spiral compound 3 are shown.

[0190] (3) Liquid nuclear magnetic resonance spectroscopy test: The synthetic products and target products in Examples 1-3 were tested by hydrogen nuclear magnetic resonance spectroscopy and carbon nuclear magnetic resonance spectroscopy using an instrument (Bruker Ascend™ 400 MHz).

[0191] The following are some examples of applications of the conjugated cyclic double-spiral compound described in this invention in solar cells:

[0192] Application Example 1

[0193] A solar cell, wherein the solar cell structure is: indium tin oxide / zinc oxide / active layer / molybdenum oxide / aluminum inverted structure.

[0194] The method for preparing the solar cell includes the following steps: After the ITO-coated glass substrate is treated with ultraviolet ozone, a thin layer of zinc oxide nanoparticles (10 mg / mL in ethanol) is spin-coated onto the glass substrate at a speed of 2500-3000 rpm for 60 seconds, and then annealed at 130°C for 10 minutes. The substrate is then transferred to a glove box, and an active layer is spin-coated at 2000 rpm for 60 seconds with a 10 mg / mL chlorobenzene solution (the active layer consists of an electron donor and an electron acceptor, with a mass ratio of 1:1; in this application example, the electron donor is PM6, and the electron acceptor is the conjugated cyclic double-spiral compound 1 provided by this invention). The substrate is then baked at 140°C for 30 minutes or, if necessary, vacuumed for 1 hour. Finally, the substrate is annealed at approximately 1 × 10⁻⁶ ppm. - 4 Under a pressure of Pa, a layer of MoO3 (20 nm) and Al (100 nm) electrode was deposited by thermal evaporation, achieving an effective area of ​​0.09 cm². 2 Components.

[0195] Application Example 2

[0196] A solar cell differs from Application Example 1 only in that the electron acceptor conjugated cyclic double-spiral compound 1 in the active layer is replaced by an equal amount of conjugated cyclic double-spiral compound 3, while the remaining experimental steps and process parameters are the same as in Application Example 1.

[0197] Comparative Example 1

[0198] A solar cell differs from Application Example 1 only in that the electron acceptor conjugated cyclic double-spiral compound 1 in the active layer is replaced by an equal amount of compound H1, while the remaining experimental steps and process parameters are the same as in Application Example 1.

[0199] Comparative Example 2

[0200] A solar cell differs from Application Example 1 only in that the electron acceptor conjugated cyclic double-spiral compound 1 in the active layer is replaced by compound H2 in equal amounts; all other experimental steps and process parameters are the same as in Application Example 1.

[0201] The structural formulas of compounds H1 and H2 in Comparative Examples 1 and 2 are as follows:

[0202]

[0203]

[0204] Performance evaluation of solar cells:

[0205] Using a luminometer (Keithely 2400) in the glove box under simulated AM 1.5G sunlight, the response data was recorded in voltage form using a lock-in amplifier (Stanford Research Systems SR830) and an IV converter (D&R-IV converter, Suzhou D&R Instruments). The test results are shown in Table 1.

[0206] Table 1

[0207]

[0208] Figure 1 The liquid UV-Vis absorption spectra of conjugated cyclic double-spiral compound 1 and conjugated cyclic double-spiral compound 3 are shown below. Figure 1 It can be seen that both conjugated cyclic double-spiral compound 1 and conjugated cyclic double-spiral compound 3 have good absorption responses in the 500-800 nm range, which is beneficial to the material's light absorption response to the solar spectrum. Figure 2 These are the thin-film UV-Vis absorption spectra of compounds 1 and 3, which have conjugated cyclic double-spiral structures. Figure 2 It can be seen that the absorption response of the compound in the thin film can be further extended to the 850 nm stage.

[0209] As can be seen from Table 1, compared with single-spiral compound, the conjugated cyclic double-spiral compound provided by this invention can obtain an ideal open-circuit voltage and effectively improve the fill factor, which is beneficial to improving the photoelectric conversion efficiency of solar cells.

[0210] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A conjugated cyclic double-spiral compound, characterized in that, The conjugated cyclic double-spiral compound includes any one of 1 to 5: 、 、 、 。 2. An organic semiconductor material, characterized in that, The organic semiconductor material is constructed using the conjugated cyclic double-spiral structure compound as described in claim 1.

3. A solar cell, characterized in that, The solar cell comprises the conjugated cyclic double-spiral compound as described in claim 1 and / or the organic semiconductor material as described in claim 2.

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