A naphthotetralin compound, a preparation method and application thereof

Abstract

The present application relates to the field of organic photovoltaic materials, and in particular to a kind of naphthotetracene compound, its preparation method and application.The present application provides a kind of naphthotetracene compound, it has the structure as shown in formula I.The compound can be applied as solid additive in the active layer of organic photovoltaic device, can effectively improve the film-forming property and crystallization performance of active layer material, can significantly improve the photovoltaic conversion efficiency of organic photovoltaic device.

Description

Technical Field

[0001] This invention relates to the field of organic photovoltaic materials, specifically to a naphthotetrabenzene compound, its preparation method, and its applications. Background Technology

[0002] Organic solar cells (OSCs), which have received increasing attention in recent years, have become an important development direction for next-generation clean and renewable energy due to their advantages such as low cost, light weight, good mechanical flexibility, and solution processing capabilities, and have broad application prospects. Driven by material innovation and device engineering, the power conversion efficiency (PCE) of single-junction organic solar cells has been improved to over 20%. Among these advancements, the morphology and structure of the active layer can effectively influence the photovoltaic conversion process. Therefore, obtaining an ideal morphology and structure is key to improving device performance.

[0003] Researchers have proposed various strategies to control the morphology of the active layer, among which the additive strategy is one of the most effective and popular, and its photovoltaic performance has been systematically studied. Among these strategies, using solid additives to adjust the morphology is a simple and effective method; for example, solid additives containing different cores such as benzene rings, thiophene, and indole are used in the construction of organic solar cells.

[0004] However, in existing technologies, traditional solid additives are mostly simple structures such as benzene rings or thiophene rings, which cannot meet the non-covalent requirements between the acceptor unit and the central donor core of the active layer. This affects the blend morphology and leads to poor photovoltaic effects such as carrier mobility and charge transfer in organic solar cells. Moreover, such active layer materials tend to spontaneously form a tightly ordered molecular stacking structure in the thin film, resulting in an excessively large phase separation size (exciton diffusion distance exceeding 10-20 nanometers), leading to excessive aggregation. This increases the probability of exciton recombination and charge trapping, reducing device efficiency.

[0005] Therefore, it is urgent to design an organic solar cell that can effectively address the scientific problems of poor film quality, severe phase separation, and strong aggregation of the active layer material itself. Summary of the Invention

[0006] To address the shortcomings of existing solid additives in organic solar cells, such as the inability to achieve good blending morphology between acceptor and donor materials in the active layer, and the lack of excellent carrier mobility and charge transfer effects, this paper presents a naphthotetraphenyl compound, its preparation method, and its applications. This compound can be used as a solid additive in the active layer of organic photovoltaic devices, effectively improving the film-forming properties and crystallinity of the active layer material. When blended with donor and acceptor materials, it can significantly enhance the photovoltaic conversion efficiency of organic photovoltaic devices.

[0007] To achieve the above objectives, the present invention provides the following technical solution.

[0008] In a first aspect, the present invention provides a naphthotetraphenyl derivative having a structure as shown in Formula I: ; Among them, R 1 and R 2 Each independently is C1-C 20 Alkyl groups or C1-C groups substituted with one or more substituents 20 The alkyl group, wherein the substituent is selected from C6-C6. 10 One or two of aryl and 5-12 heteroaryl groups; wherein the heteroatom in the 5-12 heteroaryl group is selected from at least one of N, O and S, and the number of heteroatoms is 1-4; R 3 and R 4 Each independently is C6-C 10 arylene, C6-C substituted with one or more substituents 10 arylene, 5-12-membered heteroarylene, or 5-12-membered heteroarylene substituted with one or more substituents; said substituents are independently C1-C2. 20 alkyl or R a C 1-6 The alkyl group; wherein the 5-12 aryl heteroatoms are selected from at least one of N, O and S, and the number of heteroatoms is 1-4.

[0009] In a second aspect, the present invention provides a method for preparing a naphthotetraphenyl compound as shown in Formula I as described in the first aspect, comprising the following steps: Under the presence of a solvent and a catalyst, the compound shown in Formula I-1 is subjected to a condensation reaction to obtain a naphthotetrabenzene compound as shown in Formula I. .

[0010] Thirdly, the present invention provides an application of the naphthotetrabenzene compound as described in the first aspect in organic photovoltaic devices.

[0011] Fourthly, the present invention provides an active layer material comprising the naphthotetraphenyl compounds as described in the first aspect.

[0012] Fifthly, the present invention provides an application of the active layer material as described in the fourth aspect in organic photovoltaic devices.

[0013] In a sixth aspect, the present invention provides an organic photovoltaic device comprising the active layer material as described in the fifth aspect.

[0014] The beneficial effects of this invention are as follows: (1) Based on the classic small molecule benzene ring and thiophene structure, this invention introduces a planar large fused ring structure to achieve a larger charge delocalization range and improve carrier mobility.

[0015] (2) The compound of the present invention, as a solid additive for the active layer material of organic photovoltaic devices, can promote the active layer material to have excellent film-forming properties and crystallinity, and significantly improve the photovoltaic conversion efficiency of organic photovoltaic devices.

[0016] (3) The preparation method of the present invention starts with inexpensive and readily available raw materials, resulting in lower preparation costs and a wider range of raw material sources. Attached Figure Description

[0017] Figure 1 The thermogravimetric curves are of the compounds prepared in Examples 9-11 of this invention.

[0018] Figure 2 The photovoltaic devices prepared using the compounds prepared in Examples 9-11 of this invention as solid additives (added at 3% wt relative to the donor PM6 mass) are as follows. JV curve.

[0019] Figure 3 The EQE curves of photovoltaic devices prepared using the compounds prepared in Examples 9-11 of this invention as solid additives (addition amount of 3% wt relative to the mass of the donor PM6) are shown.

[0020] Figure 4 This is a route diagram for the preparation of the compound. Detailed Implementation

[0021] The present invention will be further described below, but these embodiments do not limit the scope of protection of the present invention in any way.

[0022] In a first aspect, the present invention provides a naphthotetraphenyl derivative having a structure as shown in Formula I: ; Among them, R 1 and R 2 Each independently is C1-C 20 Alkyl groups or C1-C groups substituted with one or more substituents 20 The alkyl group, wherein the substituent is selected from C6-C6. 10 One or two of aryl and 5-12 heteroaryl groups; wherein the heteroatom in the 5-12 heteroaryl group is selected from at least one of N, O and S, and the number of heteroatoms is 1-4; R 3 and R 4Each independently is C6-C 10 arylene, C6-C substituted with one or more substituents 10 arylene, 5-12-membered heteroarylene, or 5-12-membered heteroarylene substituted with one or more substituents; said substituents are independently C1-C2. 20 alkyl or R a C 1-6 The alkyl group; wherein the 5-12 aryl heteroatoms are selected from at least one of N, O and S, and the number of heteroatoms is 1-4.

[0023] In one particular scheme, R 1 and R 2 In the middle, each C1-C 20 The alkyl group is independently C5-C 20 Alkyl groups, preferably C5-C 10 The alkyl group is more preferably n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, tert-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isoheptyl, isooctyl, isonyl, isodecyl or -CH2CH(C4H9)(C2H5).

[0024] In one particular scheme, R 1 and R 2 In the middle, each C6-C 10 The aryl group can be phenyl or naphthyl.

[0025] In one particular scheme, R 1 and R 2 In each of the 5-12 membered heteroaryl groups, the heteroatom is selected from at least one of N and S, and the number of heteroatoms is one or two; preferably, the 5-12 membered heteroaryl group is a 5-9 membered heteroaryl group, the heteroatom is N or S, and the number of heteroatoms is one; more preferably, it is a 5- or 6-membered monocyclic heteroaryl group, and even more preferably, it is a pyridyl group. or .

[0026] In one scheme, the R 3 and R 4 In the middle, each C6-C 10 Each arylene group is independently phenylene or naphthylene.

[0027] In one scheme, the R 3 and R 4 In each of the 5-12 nucleotide heteroaryl groups, the heteroatom is selected from at least one of N and S, and the number of heteroatoms is one or two; preferably, the 5-12 nucleotide heteroaryl group is a 5-9 nucleotide heteroaryl group, the heteroatom is N or S, and the number of heteroatoms is one; more preferably, it is a 5- or 6-membered monocyclic heteroaryl group, and even more preferably... , or .

[0028] In one particular scheme, R a It can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, preferably methyl.

[0029] In one scheme, the R 1 and R 2 Each independently is C1-C 20 Alkyl groups.

[0030] In one particular scheme, R 3 and R 4 Each of the substituents is independently a C6 arylene ring or a 5-12 membered heteroarylene ring substituted with one or more substituents; the substituents are independently C1-C1. 20 alkyl or In the 5-12 heteroaryl group, the heteroatom is selected from at least one of N, O and S, and the number of heteroatoms is 1-4.

[0031] In one scheme, the R 1 and R 2 Each is independently -CH2CH(C4H9)(C2H5).

[0032] In one scheme, the R 3 and R 4 Each independently , , , , by one or more C1-C 20 Alkyl-substituted , , or by one or more Replacement , , .

[0033] In one scheme, the R 3 and R 4 Each independently , , , , , , , , , , , , or Preferred , or .

[0034] In one of the solutions, It is -COOCH3.

[0035] In one embodiment, the compound represented by Formula I has any of the following structures: , or .

[0036] The compounds of Formula I of the present invention introduce substituted or unsubstituted C1-C 20 Modification with alkyl groups (e.g., 2-ethylhexane) allows for easy adjustment of solubility while improving the film-forming properties of small molecule materials. Furthermore, introducing aromatic rings (e.g., benzene, N-hexylpyrrole, or methylthiophene-3-carboxylic acid ester) as bridging groups into the structure shown in Formula I can significantly enhance the dipole moment of the molecule and create stronger intermolecular interactions and tighter π-π stacking between the small molecule material and the active layer material. Moreover, the interactions between the various structures in the molecule can form strong ICT interactions, enhancing charge transport performance.

[0037] In a second aspect, the present invention provides a method for preparing naphthotetraphenyl compounds as described in the first aspect, comprising the following steps: Under the presence of a solvent and a catalyst, the compound shown in Formula I-1 is subjected to a condensation reaction to obtain a naphthotetrabenzene compound as shown in Formula I. .

[0038] In one embodiment, the solvent is a halogenated hydrocarbon solvent, preferably chloroform.

[0039] In one embodiment, the catalyst is pyridine.

[0040] In one embodiment, the reactants in the condensation reaction are the compound shown in Formula I-1 and difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile.

[0041] In one embodiment, the condensation reaction is a Knoevenagel condensation reaction.

[0042] In one embodiment, the preparation method requires separation and purification after the condensation reaction.

[0043] Thirdly, the present invention provides an application of the naphthotetrabenzene compound as described in the first aspect in organic photovoltaic devices.

[0044] In one embodiment, the application is in organic solar cells, organic field-effect transistors, organic light-emitting diodes, or organic near-infrared photovoltaic detector devices.

[0045] In one embodiment, the naphthotetrabenzene compound is used as a solid additive in the active layer of an organic photovoltaic device; preferably, it is an n-type solid additive.

[0046] Fourthly, the present invention provides an active layer material comprising the naphthotetraphenyl compounds as described in the first aspect.

[0047] In one embodiment, the thickness of the active layer material is 60-200 nm, preferably 80-150 nm; more preferably 100-150 nm.

[0048] In one embodiment, the active layer material further includes a donor material, an acceptor material, and a solvent.

[0049] In a preferred embodiment, the active layer material is composed of a donor material, an acceptor material, a naphthotetrabenzene compound as shown in Formula I, and a solvent.

[0050] In this invention, the donor material in the active layer material can be a donor material conventionally used in organic solar cells, preferably selected from at least one of polymer donors, small molecule donors and oligomer donors, and more preferably selected from at least one of P3HT, PTB7, PM6, D18, PBDB-T, PM7 and BTR.

[0051] In this invention, the acceptor material in the active layer material can be a conventional acceptor material used in organic solar cells, preferably a small molecule acceptor, and more preferably at least one selected from L8-BO, BTP-eC9 and N2200.

[0052] In one embodiment, the solvent in the active layer material is an organic solvent, preferably a halogenated hydrocarbon solvent; more preferably chloroform.

[0053] In one embodiment, the mass ratio of the naphthotetraphenyl compound to the donor material in the active layer material is (0.01~0.1):1, preferably (0.01~0.05):1, more preferably 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, or any value within the range of any two ratios.

[0054] In one embodiment, the mass ratio of the donor material to the acceptor material in the active layer material is 1:(1~5), preferably 1:(1.2~3), more preferably 1:1, 1:1.2, 1:2, 1:3, 1:4, 1:5 or any value within the range of any two ratios.

[0055] In one embodiment, the concentrations of the donor material, the acceptor material, and the naphthotetraphenyl compound in the active layer material are 10-30 mg / mL, preferably 15-20 mg / mL, for example 10 mg / mL, 15 mg / mL, 16 mg / mL, 17 mg / mL, 18 mg / mL, 19 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, or any two of the above values.

[0056] In this invention, the active layer material is prepared using conventional methods in the art.

[0057] Preferably, the active layer material is obtained by mixing, spin-coating, and annealing the donor material, the acceptor material, and the additive in a solvent.

[0058] Preferably, the solvent is chloroform; The hybrid spin coating is preferably performed at 2000-3500 rpm for 10-100 s, more preferably at 2900 rpm for 40 s; The hybrid spin coating is preferably 60~200nm, more preferably 80~150nm; and even more preferably 100~150nm. The annealing temperature is preferably 50~100°C, more preferably 60~90°C, for example 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or any two of the above values.

[0059] Fifthly, the present invention provides an application of the active layer material as described in the fourth aspect in organic photovoltaic devices.

[0060] In one embodiment, the organic photovoltaic device is selected from at least one of organic solar cells, organic field-effect transistors, organic light-emitting diodes, and organic near-infrared photovoltaic detectors.

[0061] In a sixth aspect, the present invention provides an organic photovoltaic device comprising the active layer material as described in the fifth aspect.

[0062] In one embodiment, the organic photovoltaic device further includes: a conductive glass anode layer, an anode interface layer, a cathode interface layer, and an electrode cathode.

[0063] In one embodiment, the anode interface layer is (2-(9H-carbazole-9-yl)ethyl)phosphonic acid.

[0064] Terminology Definition Unless otherwise stated, the terms used in this invention have the following definitions, and the definitions of terms not referred to below are as commonly understood by those skilled in the art.

[0065] " at the end of the structural fragment" This means that the structural segment is connected to the rest of the molecule through this site. For example, It refers to phenylene, without a fixed substitution site.

[0066] The term "alkyl" refers to a saturated, straight-chain or branched monovalent hydrocarbon group having a specified number of carbon atoms. For example, C1-C 20 Alkyl groups refer to alkyl groups having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20), and for example, C1-C2. 20 Alkyl groups, for example, C1-C 18 Alkyl groups. Examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0067] The term "aryl" refers to an aryl group having a specified number of carbon atoms (e.g., C6-C). 10 A cyclic, aromatic monovalent hydrocarbon group, which can be monocyclic or bicyclic (e.g., two). In the case of a bicyclic ring, the monocyclic rings share two atoms and one bond. For example, C6-C. 10 Aryl groups, including but not limited to phenyl or naphthyl groups.

[0068] The term "heteroaryl" refers to a monocyclic, aromatic, monovalent group having a specified number of ring atoms (e.g., 5-12), a specified number of heteroatoms (e.g., 1, 2, 3, 4, or 5), and a specified type of heteroatom (one or more of N, O, and S). The heteroaryl group is attached to the rest of the molecule via a carbon atom or a heteroatom. Examples include 5-12-membered heteroaryls, and 5-6-membered heteroaryls with one or two nitrogen or sulfur heteroatoms. Specific examples include, but are not limited to: , or ).

[0069] Generally, the term "substituted" indicates that one or more hydrogen atoms in a given structure are substituted by a specific substituent. Further, when the group is substituted by more than one of the substituents, the substituents are independent of each other; that is, the more than one substituent can be different or the same. Unless otherwise indicated, a substituent can be substituted at each substituted position of the substituted group. When more than one position in a given structural formula can be substituted by one or more substituents selected from a specific group, the substituents can be substituted at the same or different positions.

[0070] The expression "a group B that is substituted by one or more groups A" means that group B can be unsubstituted or substituted by one or more groups A.

[0071] When a listed substituent does not specify which atom it is attached to in a compound included but not specifically mentioned in the general chemical formula, such a substituent may be bonded to any of its atoms. Combinations of substituents and / or their variants are permitted only if such combinations produce stable compounds.

[0072] When a group listed does not explicitly indicate that it has a substituent, it refers only to a group that is not substituted.

[0073] Furthermore, it should be noted that, unless otherwise explicitly stated, the descriptive phrase "...independently" used in this invention should be interpreted broadly, meaning that the described entities are independent of each other and can independently be the same or different specific functional groups. More specifically, the descriptive phrase "...independently" can mean either that the specific options expressed by the same symbol in different functional groups do not affect each other, or that the specific options expressed by the same symbol in the same functional group do not affect each other.

[0074] The terms “one or more” or “one or more kinds” refer to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

[0075] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0076] The reagents and raw materials used in this invention are all commercially available.

[0077] Specific embodiments of the present invention are as follows: The synthesis scheme of the present invention is as follows: Synthesis of n-type organic semiconductor material N-C6: Under ice bath conditions, 5-bromo-1H-pyrrole-2-carboxaldehyde was dissolved in DMF, and NaH was gradually added to the reaction system while stirring for 30 minutes. Then, 1-bromohexane was added dropwise to the mixture. Under heating conditions, a nucleophilic substitution reaction was carried out with isooctane to synthesize crude N-C6 with n-hexyl side chains, which was purified by column chromatography.

[0078] Synthesis of n-type organic semiconductor material 1-1: 4,10-dibromonaphtho[7,8,1,2,3-nopqr]tetraphenyl-6,12-dione under heating conditions with sodium hydroxide solution and sodium dithionite under nucleophilic substitution reaction was synthesized to obtain the crude product of compound 1-1 with isooctyl side chain, which was then purified by column chromatography.

[0079] Synthesis of n-type organic semiconductor material 1-2: Intermediate 1-1, in the presence of bis(pinacol)-diboron and potassium acetate solution, was catalyzed by [1,1'-bis(diphenylphosphine)-ferrocene]palladium(II) chloride. Miyaura The crude products of compounds 1-2 were synthesized by boronic acid esterification reaction, and purified by column chromatography.

[0080] Synthesis of n-type organic semiconductor material 1-3: Taking the synthesis of 1-3-1 as an example: Compound 1-2 reacts with bromobenzene in toluene as a solution and tetraphenylphosphine palladium as a catalyst, undergoing... Suzuki The crude product of compound 1-3-1 was synthesized by coupling reaction, and the pure product was obtained by column chromatography.

[0081] Synthesis of n-type organic semiconductor material 1-4: Taking the synthesis of 1-4-1 as an example: Under ice bath conditions, compound 1-3-1 was dissolved in 1,2-dichloroethane and stirred for 30 minutes under ice bath conditions. Freshly prepared compound was then gradually added dropwise. Vilsmeier-Haack reagents, occurrence Vilsmeier-Haack The reaction synthesized a crude product of compound 1-4-1, which was then purified by column chromatography.

[0082] Synthesis of n-type organic semiconductor material NP-Be: Compound 1-4-1 and difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile were dissolved in chloroform, and the reaction was carried out under pyridine catalyst. Knoevenagel The crude product of compound NP-Be was synthesized by condensation reaction, and the pure product was obtained by column chromatography and recrystallization.

[0083] Synthesis of n-type organic semiconductor material NP-Py: Compound 1-3-2 and difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile were dissolved in chloroform, and the reaction was carried out under pyridine catalyst. Knoevenagel The crude product of compound NP-Py was synthesized by condensation reaction, and the pure product was obtained by column chromatography and recrystallization.

[0084] Synthesis of n-type organic semiconductor material NP-Th: Compound 1-4-2 and difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile were dissolved in chloroform, and the reaction was carried out under pyridine catalyst. Knoevenagel The crude product of compound NP-Th was synthesized by condensation reaction, and the pure product was obtained by column chromatography and recrystallization.

[0085] In this invention, n-type organic semiconductor materials 1 The structure was identified by measuring the 1H NMR spectra using a Bruker Dex-400 NMR instrument.

[0086] Example 1 Synthesis of 5-bromo-1-hexyl-1H-pyrrole-2-carboxaldehyde (N-C6):

[0087] 5-Bromo-1H-pyrrole-2-carboxaldehyde (1.00 g, 5.75 mmol) was dissolved in DMF (30 mL). NaH (137.92 mg, 5.75 mmol) was gradually added to the reaction mixture at 0 °C, and the mixture was stirred for 30 minutes. Then, 1-bromohexane (4.02 mL, 28.74 mmol) was added dropwise to the mixture. The reaction mixture was heated at 60 °C for 12 hours. The reaction solution was quenched with water, and the aqueous phase was extracted three times with ethyl acetate. After removing the solvent by vacuum concentration, the solution was purified with petroleum ether / ethyl acetate. v / v The compound N-C6 was purified by column chromatography using a 6:1 ratio as the developing solvent to obtain a yellow oily liquid, yielding 83.5%. 1 H NMR (400 MHz, Chloroform- d ) δ 9.33 (s, 1H), 6.87 (d, J = 4.4 Hz, 1H), 6.28 (d, J = 4.1 Hz,1H), 4.38 - 4.33 (m, 2H), 1.70 - 1.63 (m, 2H), 1.30 (d, J = 9.8 Hz, 6H), 0.86(t, J = 6.5 Hz, 3H). Example 2 Synthesis of 4,10-dibromo-6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3-pentacyclo]tetraphenyl(1-1):

[0088] Under a nitrogen atmosphere, 4,10-dibromonaphtho[7,8,1,2,3-nopqr]tetraphenyl-6,12-dione (1.00 g, 2.15 mmol), sodium hydroxide solution (0.1 M, 30 mL, 3 mmol), and sodium bisulfite (1.33 g, 6.46 mmol) were added dropwise to a two-necked flask. Then, 1-bromo-2-ethylhexane (2.08 g, 1.92 mL, 10.77 mmol) was added dropwise to the mixture, and the mixture was heated at 80 °C for 24 hours. After removing the reaction solvent, 100 mL of methanol was added, and the precipitate was collected by filtration. After concentrating under reduced pressure to remove the solvent, the developing solvent was petroleum ether / ethyl acetate. v / v The mixture was diluted 20:1 to give compound 1-1. It was an orange solid, yielding 58.2%. 1 H NMR (400 MHz, CDCl3) δ 8.65 (d, J = 8.2 Hz, 2H), 8.62 (s, 2H), 8.54 (d, J = 7.5 Hz, 2H), 8.13 (t, J = 7.9 Hz, 2H), 4.14 (d, J = 5.5 Hz, 4H),2.08 - 2.03 (m, 2H), 1.93 - 1.88 (m, 2H), 1.83 - 1.71 (m, 6H), 1.25 (s, 8H),1.15 (d, J = 7.4 Hz, 6H), 1.05 (d, J = 6.8 Hz, 6H). Example 3 2,2'-(6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3- nopqr Synthesis of tetraphenyl-4,10-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentane) (1-2)

[0089] Under a nitrogen atmosphere, compound 1-1 (1.0 g), bis(pinacol)-diboron (1.47 g, 5.79 mmol), [1,1'-bis(diphenylphosphine)-ferrocene]palladium(II) chloride (42.38 mg, 0.58 mmol), and potassium acetate (0.427 g, 4.34 mmol) were sequentially added to a two-necked reaction flask, dissolved in toluene (30 mL), and the mixture was heated at 85 °C for 24 hours. The reaction solution was quenched with saturated sodium chloride solution, the aqueous phase was extracted three times with ethyl acetate, the solvent was removed by vacuum concentration, and the solution was then purified with petroleum ether / ethyl acetate. v / v The solvent (60:1) was used as the developing solvent for column chromatography purification to obtain compounds 1-2. The product was an orange solid, yield: 42.3%. 1 H NMR (400 MHz, CDCl3) δ 9.18 (s, 2H), 9.09 (d, J = 7.4 Hz, 2H), 8.78 (d, J = 8.1 Hz, 2H), 8.18 (t, J = 7.8 Hz, 2H), 4.29 (d, J = 5.4 Hz, 4H),2.17 - 2.13 (m, 2H), 2.01 - 1.97 (m, 2H), 1.85 (ddd, J = 16.2, 12.0, 7.2 Hz, 6H), 1.52 (s, 24H), 1.25 (s, 8H), 1.19 (t, J = 6.9 Hz, 6H), 1.00 (d, J = 6.8Hz, 6H). Example 4 Synthesis of 6,12-bis((2-ethylhexyl)oxy)-4,10-diphenylnaphtho[7,8,1,2,3-pentabenzo]tetraphenyl(1-3-1)

[0090] Compounds 1-2 (500 mg), potassium carbonate (440.31 mg, 3.19 mmol), tetraphenyldiphenylphosphine palladium [Pd(PPh3)4] (29.45 mg, 25.49 μmol), and 4-bromobenzene (308.48 mg, 192.80 μL, 1.40 mmol) were added to a toluene (30 mL) solution, and the mixture was heated at 110 °C for 24 hours. The mixture was cooled to room temperature, the reaction solution was quenched with saturated sodium chloride solution, the aqueous phase was extracted three times with dichloromethane, the solvent was removed by vacuum concentration, and the solution was then treated with petroleum ether / dichloromethane (…). v / v The compound 1-3-1 was purified by column chromatography using a 2:1 ratio as the developing solvent to obtain a yellow solid, yield: 39.8%. 1 H NMR (400 MHz, CDCl3) δ 8.82 (s, 2H), 8.49 - 8.41 (m, 2H), 8.23 ​​(d, J = 4.7 Hz, 2H), 8.09 (d, J = 8.0 Hz, 2H), 7.77 (t, J = 7.1 Hz, 4H), 7.60 (d, J = 7.4 Hz, 4H), 7.54 (d, J = 7.4 Hz, 2H), 4.28 (d, J = 5.4 Hz, 4H), 4.11 (q, J = 7.1 Hz,2H), 2.04 (s, 2H), 1.46 (d, J = 6.9 Hz, 4H), 1.40 - 1.35 (m, 4H), 1.25 (s,4H), 1.08 (d, J = 7.0 Hz, 6H), 1.00 (d, J = 6.9 Hz, 2H), 0.89 (d, J = 7.0 Hz, 6H). Example 5 Synthesis of 5,5'-(6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3-nopqr]tetraphenyl-4,10-diyl)bis(1-hexyl-1H-pyrrole-2-carboxaldehyde)(1-3-2)

[0091] The experimental procedure was the same as in Example 4, except that bromobenzene was replaced with N-C6. Compound 1-3-2 was a yellow solid, with a yield of 48.1%. 1 H NMR (400 MHz, CDCl3) δ 9.33 (s, 2H), 8.83 (dd, J = 8.0, 3.2 Hz, 2H), 8.50 (d, J = 3.5 Hz, 2H), 8.13 (dt, J = 8.0, 4.0 Hz, 2H), 7.69 (d, J = 3.5Hz, 2H), 6.86 (d, J = 3.8 Hz, 2H), 6.27 (d, J = 3.8 Hz, 2H), 4.36 (t, J = 7.5Hz, 4H), 4.04 (s, 4H), 3.23 (d, J = 5.8 Hz, 4H), 2.44 (d, J = 5.8 Hz, 4H), 1.99 (d, J = 5.7 Hz, 4H), 1.87 (d, J = 6.9 Hz, 2H), 1.68 (d, J = 6.0 Hz, 6H),1.28 (s, 10H), 1.14 (d, J = 5.2 Hz, 4H), 1.04 (s, 6H), 0.87 (m, 12H). Example 6 Dimethyl 2,2'-(6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3- nopqr Synthesis of tetraphenyl-4,10-diyl)bis(thiophene-3-carboxylate) (1-3-3)

[0092] The experimental procedure was the same as in Example 4, except that bromobenzene was replaced with methyl 2-bromothiophene-3-carboxylic acid. Compound 1-3-3 was a yellow solid, 42.3%. 1 H NMR (400 MHz, CDCl3) δ 8.79 (d, J = 8.0 Hz, 2H),8.52 (s, 2H), 8.09 (t, J = 7.8 Hz, 2H), 7.99 (d, J= 7.3 Hz, 2H), 7.76 (d, J =5.4 Hz, 2H), 7.50 (d, J = 5.4 Hz, 2H), 4.32 - 4.28 (m, 4H), 3.41 (s, 6H), 2.09(dd, J = 11.4, 5.4 Hz, 2H), 1.74 - 1.70 (m, 4H), 1.41 (dd, J = 9.5, 7.1 Hz, 6H), 1.08 (t, J = 7.3 Hz, 6H), 0.96 - 0.88 (m, 12H). Example 7 Synthesis of 4,4'-(6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3-nopqr]tetraphenyl-4,10-diyl)dibenzaldehyde (1-4-1)

[0093] Compound 1-3-1 (100 mg) was dissolved in 1,2-dichloroethane (15 mL) under a nitrogen atmosphere. The solution was stirred at 0 °C for 30 minutes. Then, fresh [substance name missing] was added dropwise to the solution at 0 °C. Vilsmeier-Haack Reagents (0.3 mL POCl3 and 0.9 mL DMF). After stirring at 0 °C for 30 minutes, the solution was heated to 65 °C and reacted for 4 hours. The mixture was cooled to room temperature, the reaction solution was quenched with saturated sodium chloride solution, the aqueous phase was extracted three times with dichloromethane, the solvent was removed by concentration under reduced pressure, and the solution was treated with petroleum ether / chloroform. v / v The compound 1-4-1 was purified by column chromatography using a 5:1 ratio as the developing solvent to obtain a red solid, yield: 75.6%. 1 H NMR (400 MHz, CDCl3) δ 9.95 (s, 2H), 8.57 (d, J = 8.2 Hz, 2H),8.53 (s, 2H), 8.47 (d, J = 7.5 Hz, 2H), 8.06 (s, 2H), 7.71 (s, 2H), 7.66 (d, J = 8.3 Hz, 4H), 4.08 (d, J = 5.3 Hz, 4H), 3.23 (d, J = 6.0 Hz, 2H), 2.44 (d, J=6.0 Hz, 2H), 2.02 (dt, J = 11.8, 5.9 Hz, 2H), 1.89 (dt, J = 14.0, 7.0 Hz, 2H), 1.76 - 1.70 (m, 2H), 1.26 (s, 6H), 1.13 (d, J = 7.4 Hz, 6H), 1.02 (d, J = 6.6Hz, 6H), 0.86 (d, J = 7.5 Hz, 12H). Example 8 Dimethyl 2,2'-(6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3- nopqr Synthesis of tetraphenyl-4,10-diyl)bis(5-formylthiophene-3-carboxylic acid ester)(1-4-2)

[0094] The experimental procedure was the same as in Example 7, except that compound 1-3-1 was replaced with 1-3-3. Compound 1-4-2 was a red solid, with a yield of 81.2%. 1 H NMR (400 MHz, CDCl3) δ 11.55 (s, 2H), 8.83 (s, 1H),8.59 (s, 2H), 8.53 (d, J = 7.8 Hz, 2H), 8.14 (s, 1H), 8.09 (s, 1H), 7.97 (s,1H), 7.75 (s, 2H), 7.52 (s, 2H), 4.30 (d, J = 4.6 Hz, 4H), 4.11 (q, J = 7.0 Hz, 2H), 4.03 (d, J = 5.0 Hz, 2H), 3.44 (m, 6H), 2.09 (d, J = 4.4 Hz, 2H), 1.69 (d, J = 6.5 Hz, 4H), 1.45 (d, J = 6.9 Hz, 6H), 1.08 (s, 6H), 0.91 (t, J = 7.3 Hz, 12H). Example 9 Synthesis of 2,2'-((2Z,2'Z)-(((6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3-nopqr]tetraphenyl-4,10-diyl)bis(4,1-phenylene))bis(methanemethylene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalonitrile (NP-Be)

[0095] Under a nitrogen atmosphere, compound 1-4-1 (100 mg) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (77.83 mg, 0.34 mmol) were dissolved in chloroform (30 mL). Then, 0.8 mL of pyridine was added, and the mixture was stirred overnight at 65 °C. After cooling to room temperature, the mixture was poured into water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate. After solvent removal by concentration under reduced pressure, the crude product was purified by silica gel column chromatography using n-hexane / dichloromethane (…). v / v Using methanol (1:1) as the eluent, and recrystallizing with methanol, the target compound NP-Be was given. It was a black solid, yield: 63.2%. 1 H NMR (400 MHz, CDCl3) δ 8.88 (d, J = 7.9 Hz, 2H), 8.58 (d, J = 3.7Hz, 2H), 8.47 - 8.35 (m, 4H), 8.17 (dd, J = 7.8, 3.5 Hz, 2H), 7.78 - 7.74 (m,4H), 7.66 - 7.56 (m, 8H), 4.32 (dd, J = 8.3, 6.2 Hz, 4H), 2.13 - 2.04 (m, 2H), 1.72 (d, J = 6.9 Hz, 4H), 1.24 (s, 12H), 1.07 (d, J = 6.7 Hz, 6H), 0.91 - 0.88(m, 6H). HRMS (ESI) m / z [M+H] + calcd for C 76 H 57 F4N4O4: 1165.4328, found: 1165.4302. Example 10 2,2'-((2Z,2'Z)-(((6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3- nopqr Synthesis of tetraphenyl-4,10-diyl)bis(1-hexyl-1H-pyrrole-5,2-diyl)bis(methylene)bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-2,1-diylidene)dicyanopropionic acid (NP-Py)

[0096] The experimental procedure was the same as in Example 9, except that compound 1-4-1 was replaced with 1-3-2. Compound NP-Py was a red solid with a yield of 72.1%. 1 H NMR (400 MHz, CDCl3) δ 8.67 (d, J = 1.5 Hz, 2H), 8.55(s, 2H), 8.49 (t, J = 8.4 Hz, 2H), 7.61 (t, J = 7.7 Hz, 2H), 7.29 (s, 2H), 7.26- 7.24 (m, 2H), 6.49 (d, J = 2.2 Hz, 2H), 4.22 - 4.07 (m, 8H), 2.03 (d, J = 1.3Hz, 4H), 1.77 (d, J = 23.9 Hz, 6H), 1.31 - 1.23 (m, 34H), 0.87 (d, J = 6.6 Hz,12H). HRMS (ESI) m / z [M+H] + calcd for C 84 H 78 F4N6O4: 1311.6093, found: 1311.6817. Example 11 Synthesis of dimethyl 2,2'-(6,12-bis((2-ethylhexyl)oxy)naphtho[7,8,1,2,3-nopqr]tetraphenyl-4,10-diyl)bis(5-(((Z)-1-(dicyanomethylene)-5,6-difluoro-3-oxo-1,3-dihydro-2H-inden-2-ylidene)methyl)thiophene-3-carboxylic acid ester)(NP-Th)

[0097] The experimental procedure was the same as in Example 9, except that compound 1-4-1 was replaced with 1-4-2. Compound NP-Th was a purple solid with a yield of 68.7%. 1 H NMR (400 MHz, ) δ 8.85 (s, 1H), 8.59 (d, J = 48.8 Hz, 2H), 8.45 (d, J = 7.1 Hz, 1H), 8.16 - 8.11 (m, 2H), 7.77 - 7.75 (m, 2H), 7.63(d, J = 1.8 Hz, 2H), 7.53 (d, J = 3.8 Hz, 2H), 7.48 - 7.46 (m, 2H), 7.23 (d, J =3.7 Hz, 2H), 4.94 (d, J = 12.3 Hz, 2H), 3.88 (d, J = 1.7 Hz, 4H), 3.85 (d, J =1.9 Hz, 4H), 1.24 (s, 19H), 0.87 (d, J = 5.3 Hz, 12H). HRMS (ESI) m / z [M+H] + calcd for C 76 H 56 F4N4O8S2: 1293.3548, found: 1293.5738. Example 12 Performance Characterization of n-type Organic Semiconductor Materials The thermal stability of the compounds prepared in Examples 9-11 was tested using a thermogravimetric analyzer.

[0098] The thermogravimetric curves of the compounds NP-Be, NP-Py, and NP-Th prepared in Examples 9-11 are shown below. Figure 1 As shown in the figure, the decomposition temperatures (5% weight loss temperatures) of NP-Be, NP-Py, and NP-Th are 278.6, 227.9, and 224.5℃, respectively.

[0099] It is evident that the compound prepared by this invention is heat-resistant and exhibits excellent thermal stability.

[0100] Example 13 Fabrication of photovoltaic devices using n-type organic semiconductor materials The structure of a photovoltaic device based on n-type organic semiconductor materials consists of an indium tin oxide (ITO) conductive glass anode layer, a 2PACz anode interface layer, an active layer, a PNDIT-F3N cathode interface layer, and an Ag electrode cathode (where each material is arranged sequentially).

[0101] In the fabrication of the photovoltaic device of the present invention, the active layer is composed of a polymer donor PM6, a small molecule acceptor L8-BO, additives, and a solvent chloroform. The additives are compounds NP-Be, NP-Py, and NP-Th, and the amount of additives is 3 wt% of the polymer donor PM6. The total concentration of the donor, acceptor, and additives in the active layer is 16 mg / mL.

[0102] At room temperature, the above-mentioned additives NP-Be, NP-Py, and NP-Th were added to a mixture of PM6 and L8-BO (PM6:L8-BO mass ratio of 1:1.2) to achieve a total concentration of 16 mg / mL for each component of the active layer. -1 Calculations were performed to obtain a blend by dissolving the compound in chloroform. The blend was then spin-coated onto ITO / 2PACz at 2900 rpm for 40 seconds, resulting in a spin-coated thickness of approximately 100 nm, yielding a uniform active layer blend film. Subsequently, the active layer film was annealed at 80°C for 5 minutes to prepare the active layer material.

[0103] Photovoltaic devices 1, 2, and 3 were prepared using conventional methods according to the above structure.

[0104] Example 14: Testing the photovoltaic performance of photovoltaic devices fabricated from n-type organic semiconductor materials. (1) For photovoltaic devices 1-3 JV Test: In a glove box filled with nitrogen (N2), a Keithley 2400 source meter and an SS-F5-3A solar simulator (AAA grade, 50×50mm) were used. 2 The performance of photovoltaic devices was measured using a beam size (solar simulator provided by Enli Technology Co., Ltd.). The active component composition of photovoltaic devices 1, 2, and 3 was as follows: a PM6:L8-BO mixing ratio of 1:1.2. w / w , 16 mg / mL), and 3% wt of NP-Be, NP-Py and NP-Th were added respectively.

[0105] Performance calculation formula: FF (fill factor) = (V m *J m ) / (V oc *J sc V ocJ is the open-circuit voltage (i.e., the voltage when J=0). sc The short-circuit current density (i.e., the current density when V=0), and the maximum power point P. max The corresponding V m J m ; Energy conversion efficiency PCE = (V oc *J sc *FF) / P in P in Standard light intensity.

[0106] Received J - V Curve graph as Figure 2 As shown: The open-circuit voltage of PM6:L8-BO photovoltaic device 1 after NP-Be treatment is 0.900 V, and the short-circuit current density is 26.73 mA cm⁻¹. -2 The fill factor is 74.98%, and the energy conversion efficiency is 17.71%. The open-circuit voltage of the PM6:L8-BO photovoltaic device 2 treated with NP-Py is 0.905 V, and the short-circuit current density is 27.08 mA cm⁻¹. -2 The fill factor is 76.13%, and the energy conversion efficiency is 18.65%. The open-circuit voltage of the PM6:L8-BO photovoltaic device 3 after NP-Th treatment is 0.913 V, and the short-circuit current density is 27.20 mA cm⁻¹. -2 The fill factor is 78.82% and the energy conversion efficiency is 19.56%.

[0107] (2) The EQE test of photovoltaic devices 1-3 was performed using the OE-R3011 solar cell spectral response measurement system (Enli Technology Co., Ltd.). The EQE curve is shown in the figure. Figure 3 As shown. This was further confirmed by external quantum efficiency (EQE) spectroscopy. JV Reliability of the tested photovoltaic parameters (see) Figure 3 The integral obtained from the EQE curves of devices 1-3. J SC The values ​​were 25.76, 25.84, and 26.12 mA cm, respectively. -2 ,and JV The results obtained from the curves are highly consistent, with an error of less than 5%.

[0108] Furthermore, the figure shows that the EQE test range is 300-1000 nm, and the NP-Th photovoltaic device has the highest EQE value at 627 nm, which is 92.44%.

[0109] Although the invention has been described in conjunction with preferred embodiments, the invention is not limited to the above embodiments, and it should be understood that the appended claims summarize the scope of the invention. Guided by the inventive concept, those skilled in the art should recognize that any modifications made to the various embodiments of the invention will be covered by the spirit and scope of the claims.

Claims

1. A naphthotetraphenyl compound, characterized in that, It has the structure shown in Equation I: ； Among them, R 1 and R 2 Each independently is C1-C 20 Alkyl groups or C1-C groups substituted with one or more substituents 20 The alkyl group, wherein the substituent is selected from C6-C6. 10 One or two of aryl and 5-12 heteroaryl groups; wherein the heteroatom in the 5-12 heteroaryl group is selected from at least one of N, O and S, and the number of heteroatoms is 1-4. R 3 and R 4 Each independently is C6-C 10 arylene, C6-C substituted with one or more substituents 10 arylene, 5-12-membered heteroarylene, or 5-12-membered heteroarylene substituted with one or more substituents; said substituents are independently C1-C2. 20 alkyl or R a It is a C1-C6 alkyl group; in the 5-12 member heteroaryl group, the heteroatom is selected from at least one of N, O and S, and the number of heteroatoms is 1-4.

2. The compound according to claim 1, characterized in that, R 1 and R 2 In the middle, each C1-C 20 The alkyl group is independently C5-C 20 Alkyl groups, preferably C5-C 10 The alkyl group is more preferably n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, tert-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isoheptyl, isooctyl, isononyl, isodecyl or -CH2CH(C4H9)(C2H5); Optionally, R 1 and R 2 In the middle, each C6-C 10 The aryl group can be phenyl or naphthyl independently; Optionally, R 1 and R 2 In each of the 5-12 membered heteroaryl groups, the heteroatom is selected from at least one of N and S, and the number of heteroatoms is one or two; preferably, the 5-12 membered heteroaryl group is a 5-9 membered heteroaryl group, the heteroatom is N or S, and the number of heteroatoms is one; more preferably, it is a 5- or 6-membered monocyclic heteroaryl group, and even more preferably, it is a pyridyl group. or ; Optionally, the R 3 and R 4 In the middle, each C6-C 10 Each arylene group is independently phenylene or naphthylene; Optionally, the R 3 and R 4 In each of the 5-12 nucleotide heteroaryl groups, the heteroatom is selected from at least one of N and S, and the number of heteroatoms is one or two; preferably, the 5-12 nucleotide heteroaryl group is a 5-9 nucleotide heteroaryl group, the heteroatom is N or S, and the number of heteroatoms is one; more preferably, it is a 5- or 6-membered monocyclic heteroaryl group, and even more preferably... , or ; Optionally, R a It can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, preferably methyl.

3. The compound according to claim 1, characterized in that, The R 1 and R 2 Each independently is C1-C 20 Alkyl groups; Optionally, R 3 and R 4 Each is an independent C6 arylene or a 5-12 membered heteroarylene substituted with one or more substituents; Preferably, the R 1 and R 2 Each is independently -CH2CH(C4H9)(C2H5); Preferably, the R 3 and R 4 Each independently , , , , by one or more C1-C 20 Alkyl-substituted , , or by one or more Replacement , , ; More preferably, the R 3 and R 4 Each independently , , , , , , , , , , , , or Preferred , or ; Preferably, It is -COOCH3.

4. The compound according to any one of claims 1-3, characterized in that, The compound represented by Formula I has any of the following structures: , or .

5. A method for preparing a naphthotetraphenyl compound according to any one of claims 1-4, comprising the following steps: Under the presence of a solvent and a catalyst, the compound shown in Formula I-1 is subjected to a condensation reaction to obtain a naphthotetrabenzene compound as shown in Formula I. ； Among them, R 1 R 2 R 3 and R 4 The definition is as described in any one of claims 1-4; Optionally, the solvent is a halocarbon solvent, preferably chloroform; Optionally, the catalyst is pyridine.

6. The application of a naphthotetrabenzene compound according to any one of claims 1-4 in organic photovoltaic devices; Preferably, the organic photovoltaic device is selected from at least one of organic solar cells, organic field-effect transistors, organic light-emitting diodes, and organic near-infrared photovoltaic detectors; Optionally, the naphthotetrabenzene compound is used as a solid additive in the active layer of the organic photovoltaic device; preferably, it is an n-type solid additive.

7. An active layer material comprising a naphthotetraphenyl compound as described in any one of claims 1-4; Optionally, the thickness of the active layer material is 60~200nm, preferably 80~150nm; more preferably 100~150nm.

8. The active layer material according to claim 7, characterized in that, The active layer material further includes a donor material, an acceptor material, and a solvent; Preferably, the mass ratio of the naphthotetraphenyl compound to the donor material is (0.01~0.1):1, more preferably (0.01~0.05):1; Preferably, the concentrations of the donor material, the acceptor material, and the naphthotetrabenzene compound in the active layer material are 10-30 mg / mL.

9. The application of the active layer material according to claim 7 or 8 in an organic photovoltaic device; Preferably, the organic photovoltaic device is selected from at least one of organic solar cells, organic field-effect transistors, organic light-emitting diodes, and organic near-infrared photovoltaic detectors.

10. An organic photovoltaic device comprising the active layer material according to claim 7 or 8.

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