Octacyclic negative curvature polycyclic aromatic hydrocarbon, synthesis method and application thereof

Abstract

This application discloses a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, its synthesis method, and its application, belonging to the field of organic synthesis. The synthesis method uses a haloacenaphthene derivative as a starting material. First, a tetrahalogenated key intermediate containing an eight-membered ring is constructed via a titanium tetrachloride-catalyzed cyclization tetramerization reaction. Subsequently, this intermediate undergoes a cyclization coupling reaction with an alkyne compound in the presence of a palladium catalyst, silver salt, and phosphine ligand to generate a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring. The synthesis method of this application avoids multi-step precursor synthesis, resulting in a concise process. It allows for the flexible introduction of functional groups such as trifluoromethyl and silyl groups, improving the solubility and processability of the material. The obtained product exhibits a non-planar configuration, a narrow optical band gap, and excellent electron transport properties, making it suitable for applications... n Applications include semiconductors, chiral optoelectronic materials, and nano-carbon materials.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, its synthesis method, and its application. Background Technology

[0002] The photoelectric properties of polycyclic aromatic hydrocarbons (PAHs) are fundamentally determined by their topological structure. Traditional all-six-membered ring PAHs suffer from strong intermolecular π-π packing due to their planar configuration, leading to problems such as concentration quenching, low solid-state luminescence efficiency, and poor solubility, severely limiting their application performance in optoelectronic devices. To overcome this bottleneck, the precise introduction of non-six-membered rings (such as seven-membered and eight-membered rings) into graphene nanostructures has become a cutting-edge research area. Among them, the introduction of eight-membered rings can effectively warp the molecular plane, forming a stable saddle-shaped three-dimensional configuration. This negative curvature structure not only effectively suppresses close intermolecular packing and significantly improves the solubility and solid-state luminescence efficiency of the material, but also induces unique electron delocalization, bringing novel photoelectric properties such as narrow band gap and high carrier mobility, showing great potential in fields such as organic semiconductors, chiral materials, and carbon nanomaterials. Therefore, developing a general synthetic strategy that is simple in steps, mild in conditions, has ideal yields, and has good functional group compatibility to achieve the efficient construction of negative curvature polycyclic aromatic hydrocarbons with different substituents and electronic properties has become an urgent technical need in this field.

[0003] Against this backdrop, a newly developed palladium-catalyzed cyclization coupling strategy has achieved the efficient construction of eight-membered rings through the ingenious design of precursor molecules. This method employs a modular design concept, achieving precise synthesis of eight-membered ring structures under relatively mild reaction conditions (e.g., 80-140℃) by rationally selecting haloaromatic precursors and alkyne coupling units. By pre-setting reaction sites, the selectivity of the cyclization process can be effectively controlled, significantly improving reaction efficiency. The use of a silver salt-mediated redox neutral pathway avoids the use of strong oxidants, enhancing compatibility with sensitive functional groups. Through ligand fine-tuning, the high-strain transition state during eight-membered ring formation can be successfully stabilized, suppressing side reactions such as ring contraction. The establishment of this efficient synthetic strategy not only provides a solid material basis for the systematic study of the structure-activity relationship of negative curvature PAHs containing eight-membered rings, solving the long-standing problem of sample availability that has hindered the development of this field, but also opens up new avenues for developing high-performance organic optoelectronic materials with narrow band gaps and high carrier mobility through precise control of molecular curvature and electronic structure. Summary of the Invention

[0004] Technical problem to be solved: This invention provides a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, its synthesis method and application, to solve the core technical problems of existing technologies, such as strong intermolecular π-π stacking caused by the planar configuration of all six-membered ring PAHs, which leads to concentration quenching, low solid-state luminescence efficiency and poor solubility, which seriously restrict their application performance in optoelectronic devices.

[0005] The purpose of this invention is to provide a method for synthesizing polycyclic aromatic hydrocarbons with negative curvature containing eight-membered rings based on a palladium-catalyzed C–H / alkyne cyclization strategy. Through a two-step core strategy of "construction of key eight-membered ring precursors" and "palladium-catalyzed cyclization extension", the invention achieves the precise and efficient construction of complex multi-eight-membered ring structures. Another purpose of this invention is to provide the application of negative curvature polycyclic aromatic hydrocarbons obtained by the above method in optoelectronic devices.

[0006] To achieve the above objectives, this application provides the following technical solution: A method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring, wherein the synthetic route for the negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring is as follows: ; Specifically, the following steps are included: Step 1: Using the haloacenaphthene derivative shown in Formula II, a cyclization tetramerization reaction is carried out in a first organic solvent under Lewis acid catalysis to obtain a tetrabromo precursor containing a single eight-membered ring as shown in Formula III; Step 2: The tetrabromo precursor containing a single eight-membered ring, as shown in Formula III, and the disubstituted alkyne undergo a one-step multiple CH / alkyne cyclization coupling reaction in a second organic solvent in the presence of a palladium catalyst, a silver salt, and a phosphine ligand to obtain a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, as shown in Formula I.

[0007] Furthermore, in the first step, the Lewis acid is titanium tetrachloride (TiCl4), the first organic solvent is o-dichlorobenzene, and the reaction temperature of the cyclization tetramerization reaction is 150-200℃.

[0008] Further, in the first step, 240-250 parts by mass of haloacenaphthene derivative, 0.6-0.8 parts of Lewis acid, and 20-40 parts of first organic solvent are prepared.

[0009] Further, in the second step, the following proportions are made by mass: 40-60 parts of a tetrabromo precursor containing a single eight-membered ring, 60-70 parts of a disubstituted alkyne, 1-2 parts of a palladium catalyst, 40-50 parts of a silver salt, 2-3 parts of a phosphine ligand, and 10-20 parts of a second organic solvent.

[0010] Furthermore, in the second step, the palladium catalyst is palladium acetate Pd(OAc)2, the silver salt is silver acetate AgOAc, and the phosphine ligand is tris(4-chlorophenyl)phosphine P(4-ClC6H4)3.

[0011] Furthermore, in the second step, the second organic solvent is 1,2-dichloroethane, and the reaction temperature is 70-90℃.

[0012] Furthermore, in the second step, the disubstituted alkyne is 1,2-diarylacetylene, wherein the aryl group in the 1,2-diarylacetylene is selected from phenyl, substituted phenyl, or naphthyl.

[0013] A negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, prepared by any of the above synthetic methods, wherein the negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring is shown in general formula (I): Formula (I), wherein R is a substituted aryl group containing C1-C12 alkyl, C1-C12 alkoxy, trifluoromethyl, silyl, amino or halogen.

[0014] This application also discloses the application of negative curvature polycyclic aromatic hydrocarbons containing eight-membered rings prepared by any of the above-mentioned synthetic methods in the preparation of optoelectronic devices.

[0015] Furthermore, the optoelectronic device is a perovskite solar cell, and the negative curvature polycyclic aromatic hydrocarbon exists as an additive in the perovskite active layer.

[0016] Explanation of the principle: This invention uses haloacenaphthene derivatives such as 3-bromoacenaphthene-1(2H)-one as key precursors. A cyclization tetramerization reaction catalyzed by titanium tetrachloride (TiCl4) efficiently constructs the initial eight-membered ring strained structure. Subsequent palladium-catalyzed Heck coupling reaction achieves the directional assembly and extension of multiple eight-membered rings through precise C / C bond formation. The introduction of tris(4-chlorophenyl)phosphine ligands can regulate the reaction pathway through steric hindrance and electronic effects, stabilizing the cyclization transition state and facilitating the precise construction of complex saddle-shaped structures. The unique saddle-shaped three-dimensional configuration of this material can... It effectively suppresses harmful π-π stacking between molecules, significantly enhancing its luminescence efficiency and solubility in the solid state. In addition, the negative curvature strain introduced by the fusion of five-membered and eight-membered rings regulates the electron cloud distribution of the conjugated system, making it exhibit a narrow optical band gap and multiple redox activities, thereby optimizing its light-harvesting ability and charge transport performance. The resulting material exhibits excellent interface stability and performance improvement when used as an additive for perovskite batteries. The saddle-shaped graphene nanomaterial is a negative curvature polycyclic aromatic hydrocarbon with a precise molecular structure composed of carbon and hydrogen elements.

[0017] This application provides a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, its synthesis method, and its application. Compared with the prior art, it has the following advantages: 1. This invention is the first to combine "cyclization tetramerization to construct an eight-membered ring module" with "palladium-catalyzed multiple cyclization extension" to form a general synthesis platform. By changing the structure (R) of the alkyne in general formula (III), the physicochemical properties of the final product (such as solubility, energy level, solid stacking, etc.) can be systematically adjusted, thereby realizing "on-demand design" of material properties and breaking through the limitation of existing methods that can only synthesize specific structures. 2. This invention avoids lengthy multi-step precursor synthesis. It can rapidly construct complex negative curvature frameworks from commercially available or readily available raw materials through two core reactions, which has extremely high step economy. The key palladium catalysis step enables the construction of four C-C bonds and closure of multiple ring systems in one step, which significantly improves the synthesis efficiency. 3. In this invention, the key palladium-catalyzed cyclization step is carried out under mild conditions (80°C) and adopts an AgOAc-mediated redox neutral pathway, avoiding the use of strong oxidants. It has good compatibility with a variety of functional groups (such as tert-butyl), and provides the possibility of introducing more functional groups (such as trifluoromethyl, silyl, etc.) to further improve the material performance. 4. This invention utilizes current density-voltage ( J - V The test system evaluated the performance of photovoltaic devices at different additive concentrations. The molecule I additive system can significantly improve the photoelectric conversion efficiency (PCE) of the device. 5. Negative curvature polycyclic aromatic hydrocarbons prepared by this general method exhibit excellent solubility due to their non-planar configuration, tunable electronic structure, and superior solubility. n It has shown broad application potential in fields such as semiconductors, chiral optoelectronic materials, and especially as an additive for perovskite solar cells; when used as an additive, it can passivate both bulk and interface defects in perovskite films, significantly improving device efficiency and stability. 6. The most significant feature of molecule I designed in this invention is that it utilizes its three-dimensional saddle-shaped configuration and multiple redox activities to simultaneously function as a "defect passivator" and an "interface bridge" in the perovskite active layer. Compared with traditional additives, this invention improves the quality and charge transport efficiency of the perovskite film in a single synergistic step, achieving synergistic optimization of device efficiency and stability. In addition, the excellent solubility and film-forming compatibility of the negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring make it very suitable for large-scale solution processing, providing a new material solution for the industrialization of perovskite photovoltaic technology. Attached Figure Description

[0018] Figure 1 The 1H NMR spectrum of the saddle-shaped molecule synthesized in this application in deuterated dichloromethane (CD2Cl2) is shown. 1 ¹H NMR spectrum, the upper figure is δA magnified view of the 1.0-8.0 ppm range is shown below. δ Magnified view of the 7.0-8.6 ppm range; Figure 2 This is the carbon NMR spectrum of the saddle-shaped molecule synthesized in this application in CD2Cl2 ( 13 C NMR spectrum, where a is the full spectrum, b is the aryl carbon region spectrum, and c is the aryl carbon region DEPT135 spectrum; Figure 3 The photovoltaic performance parameters of perovskite solar cells are as follows: the negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring synthesized in this application is added as an additive. Among them, a is the open circuit voltage diagram, b is the short circuit current density diagram, c is the fill factor diagram, and d is the photoelectric conversion efficiency diagram. Figure 4 The external quantum efficiency (EQE) curves of the device using an eight-membered ring-containing negative curvature polycyclic aromatic hydrocarbon as an additive, synthesized in this application, are shown. Figure 5 These are the matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) spectra (solid lines) and data simulation spectra (dashed lines) of this application. Figure 6 These are the UV-Vis absorption (solid line) spectrum and fluorescence (dashed line) spectrum of this application. Detailed Implementation

[0019] The synthetic method provided by this invention constitutes a general synthetic platform. Its core advantage lies in the ability to efficiently and modularly synthesize a series of polycyclic aromatic hydrocarbons (PAHs) of the eight-membered ring with negative curvature and different substituents, electronic properties, and solubility by modifying the structure of disubstituted alkynes. The following examples will help those skilled in the art to further understand this invention, but do not limit the invention in any way. Those skilled in the art can flexibly select alkyne monomers with different aryl groups according to the performance requirements of the target product, thereby achieving precise customization of the final molecular structure. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of this invention, and these all fall within the scope of protection of this invention.

[0020] Example 1: This example provides a method for synthesizing a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring. The synthetic route for the negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring is as follows: ; Includes the following steps: Step 1: Using the haloacenaphthene derivative shown in Formula II, a cyclization tetramerization reaction is carried out in a first organic solvent under Lewis acid catalysis to obtain a tetrabromo precursor containing a single eight-membered ring as shown in Formula III; Step 2: The tetrabromo precursor containing a single eight-membered ring, as shown in Formula III, and the disubstituted alkyne undergo a one-step multiple CH / alkyne cyclization coupling reaction in a second organic solvent in the presence of a palladium catalyst, a silver salt, and a phosphine ligand to obtain a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, as shown in Formula I.

[0021] The method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring specifically includes the following steps: S1. Using 7.7 g (41.8 mmol) of commercially available 3,4-dihydronaphthyl-2(1H)-one (compound 1) as the starting material, dissolved in 40 mL of chloroform, and under nitrogen protection at 0°C, slowly added dropwise 11.3 g (41.8 mmol) of phosphorus tribromide and 3.1 g (41.8 mmol) of phosphorus tribromide. N , N A mixed solution of dimethylformamide (DMF) was reacted for 1 hour, and after post-treatment, compound 2 was obtained with a yield of approximately 85%. Subsequently, compound 2 was dissolved in 30 mL of toluene, and 16.2 g (71.2 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was added. The mixture was stirred at 100 °C for 48 hours, and after purification, the aromatized product 2-bromo-1-naphthaldehyde (compound 3) was obtained with a yield of approximately 80%. Next, compound 3 was dissolved in 20 mL of ethanol, and 1.1 g (28.4 mmol) of sodium borohydride was added in portions under ice bath cooling at 0 °C. After reacting for 1 hour, the product was processed to obtain alcohol intermediate 4 with a yield of approximately 93%. Then, alcohol intermediate 4 was reacted with 6.0 g (22.1 mmol) of phosphorus tribromide in 20 mL of chloroform at 55 °C for 8 hours to convert to brominated product 5 with a yield of approximately 80%. Finally, brominated product 5 was reacted with 10 mL of chloroform... The nitrile derivative 6 was reacted with 1.8 g (27.7 mmol) potassium cyanide in mL of DMF at 80 °C for 8 hours to give nitrile derivative 6 in a yield of approximately 66%. Finally, nitrile 6 was hydrolyzed in 15 mL of a 4:1 (v / v) ethanol / water mixture containing 1.6 g (28.4 mmol) potassium hydroxide under reflux at 80 °C for 24 hours. After the reaction, the nitrile was acidified, extracted with dichloromethane, dried, and concentrated, and then purified by silica gel column chromatography to finally obtain 2.66 g (10.0 mmol) of the target carboxylic acid compound 7, with an overall yield of approximately 72%. ; S2. 2.66 g of 2-(2-bromonaphth-1-yl)acetic acid and 8 mL of thionyl chloride (SOCl2) were heated under nitrogen protection and refluxed in an oil bath at 85°C for 1 hour to carry out acylation. After the reaction was completed, excess SOCl2 was completely removed by vacuum distillation to obtain the oily intermediate 2-(2-bromonaphth-1-yl)acetyl chloride (compound 8). S3. Compound 8 was added in portions of 2.66 g of aluminum trichloride (AlCl3) to 10 mL of dichloromethane (DCM) at 0 °C. The mixture was stirred at 0 °C for 30 min to carry out Friedel-Crafts acylation. The mixture was then refluxed for 30 min to construct a pentacyclic system. The glacial hydrochloric acid used to quench the Friedel-Crafts acylation reaction was obtained by mixing 100 g of ice with 10 mL of concentrated hydrochloric acid. The mixture was extracted with DCM (3 × 50 mL). The organic phase was dried over anhydrous Na2SO4 and concentrated. The organic phase was purified by silica gel column chromatography to obtain a white solid intermediate 3-bromoacenaphthene-1(2H)-one (compound 9). The eluent was n-hexane / DCM = 1:1. The yield of compound 9 was 1.71 g, with a yield of 69%. S4. Dissolve 247.09 mg of compound 9 in 20 mL of o-dichlorobenzene to prepare solution A. Separately, add 0.68 mL of titanium tetrachloride (TiCl4) to 20 mL of o-dichlorobenzene and heat to reflux under nitrogen protection to prepare solution B. Under continuous stirring and a nitrogen atmosphere, add solution A dropwise to the refluxed solution B to carry out cyclization tetramerization. React at 180 °C for 1-2 hours. After the reaction is completed, quench the reaction with a mixture of concentrated hydrochloric acid and ice. The crude product is purified by silica gel column chromatography (eluent: dichloromethane / n-hexane = 1 / 4) to give 41.24 mg of a brown solid product containing a single eight-membered ring, a tetrabromo precursor (compound 10), with a yield of 18%. S5. 50 mg of a tetrabromo precursor compound containing a single eight-membered ring, 69.74 mg of 1,2-bis(4-tert-butylphenyl)acetylene, 40.07 mg of silver acetate (AgOAc), 1.84 mg of palladium acetate (Pd(OAc)2), and 2.99 mg of tris(4-chlorophenyl)phosphine (P(4-ClC6H4)3) were dissolved in 10 mL of 1,2-dichloroethane (DCE). The mixture was stirred at 80 °C for 36 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was concentrated, and the crude product was purified by silica gel column chromatography (eluent: dichloromethane / n-hexane = 1 / 3) to obtain a dark brown solid product HM. The final target product was obtained with a mass of 25.6 mg (17.46 μmol), with a yield of 32%.

[0022] The material described in this invention has a unique three-dimensional topological structure composed of carbon and hydrogen atoms with four pairs of continuous five- to eight-membered rings (5-8) cores, exhibiting a curved saddle-shaped configuration. Furthermore, this non-planar molecular skeleton has abundant electron delocalization induced by ring strain and a specific alternating bond length structure.

[0023] The aforementioned saddle-shaped negative curvature graphene nanomaterial (HM) is used as an additive in perovskite solar cells or as a material in organic optoelectronic functional layers.

[0024] In Example 2, under nitrogen protection, 10.0 g (24.7 mmol) of 2,6-dibromoanthraquinone, 7.5 g (30.0 mmol) of 1,3-diphenyl-2-propanone, and 100 mL of anhydrous ethanol were added to a 250 mL three-necked flask, and the mixture was stirred until the solids were completely dissolved. The reaction system was cooled and maintained below 30 °C, and then a solution of potassium hydroxide (5.0 g, 89.0 mmol) in anhydrous ethanol was slowly added dropwise. After the addition was complete, the reaction mixture was heated to 80 °C and refluxed for 20 minutes. After the reaction was complete, the mixture was cooled to room temperature and quenched in 200 mL of ice water, resulting in the precipitation of a large amount of solid. The solid was collected by suction filtration, and the filter cake was washed with a small amount of cold ethanol and dried under vacuum to obtain an anthrone intermediate with a mass of 8.1 g, yielding 85%. Under nitrogen protection, 2,5-dibromonaphthalene (5.0 g, 17.6 mmol) and toluene (100 mL) were added to anthrone intermediate (8.1 g, 17.3 mmol). The reaction mixture was heated to 120 °C and refluxed with stirring for 48 hours, during which the reaction progress was monitored by thin-layer chromatography (TLC). After the reaction was completed, the mixture was cooled to room temperature, and the toluene solvent was removed by vacuum distillation. The resulting residue was dissolved in dichloromethane, and the organic phase was washed successively with saturated brine (3 × 50 mL) and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane, v / v ratio 5:1) to obtain the purified target molecule. The mass was 7.1 g, and the yield was 70%.

[0025] In Example 3, under nitrogen protection, 1,8-dibromonaphthalene (2.86 g, 10.0 mmol), 9-anthraboronic acid (3.03 g, 12.0 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 578 mg, 0.50 mmol), and potassium carbonate (K2CO3, 4.14 g, 30.0 mmol) were added sequentially to a 250 mL two-necked flask. After purging with nitrogen three times, a mixed solvent of degassed toluene (60 mL), ethanol (20 mL), and deionized water (20 mL) was added under nitrogen atmosphere. The reaction mixture was heated to 90 °C and refluxed with vigorous stirring at this temperature for 18 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into 200 mL of ice water, and extracted with dichloromethane (3 × 100 mL). The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / dichloromethane (10:1 v / v) as the eluent to give a white, flaky solid, 9-(8-bromonaphth-1-yl)anthracene. Under nitrogen protection, 9-(8-bromonaphth-1-yl)anthracene (780 mg, 2.0 mmol), 1,2-bis(4-tert-butylphenyl)acetylene (361 mg, 1.1 mmol), palladium acetate (Pd(OAc)2) (13.4 mg, 0.06 mmol), tris(4-chlorophenyl)phosphine (P(4-ClC6H4)3) (34.2 mg, 0.09 mmol), and silver acetate (AgOAc) (400 mg, 2.4 mmol) were successively dissolved in anhydrous, degassed 1,2-dichloroethane (DCE) (40 mL). The reaction mixture was placed in an oil bath at 85 °C and stirred under nitrogen atmosphere in the dark for 60 hours. After the reaction was complete, the mixture was cooled to room temperature and filtered through a diatomaceous earth short column to remove insoluble solids. The filtrate was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography using dichloromethane / n-hexane (gradient elution, volume ratio gradually changing from 1:4 to 1:1) as the eluent, yielding a dark green solid. .

[0026] In Example 4, under nitrogen protection, 1,8-dibromonaphthalene (2.86 g, 10.0 mmol), anthracene-10-ylboronic acid pinacol ester (3.92 g, 11.0 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 578 mg, 0.50 mmol), and cesium carbonate (Cs2CO3, 6.52 g, 20.0 mmol) were added sequentially to a 250 mL two-necked flask. After purging with nitrogen three times, a mixed solvent of degassed toluene (80 mL) and deionized water (20 mL) was added under nitrogen atmosphere. The reaction mixture was heated to 95 °C and refluxed with vigorous stirring at this temperature for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, poured into 200 mL of ice water, and extracted with dichloromethane (3 × 100 mL). The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / dichloromethane (15:1 v / v) as the eluent to give a white solid 10-(8-bromonaphth-1-yl)-9,9'-bianthracene. Under nitrogen protection, 10-(8-bromonaphth-1-yl)-9,9'-bianthracene (1.12 g, 2.0 mmol), 1,2-diphenylacetylene (196 mg, 1.1 mmol), palladium acetate (Pd(OAc)2) (13.4 mg, 0.06 mmol), tris(4-chlorophenyl)phosphine (P(4-ClC6H4)3) (34.2 mg, 0.09 mmol), and silver acetate (AgOAc) (400 mg, 2.4 mmol) were successively dissolved in anhydrous degassed 1,2-dichloroethane (DCE) (40 mL). The reaction mixture was placed in a 90°C oil bath and stirred under nitrogen atmosphere in the dark for 72 hours. After the reaction was complete, the mixture was cooled to room temperature and filtered through a short diatomaceous earth column to remove insoluble solids. The filtrate was concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography using dichloromethane / n-hexane (gradient elution, volume ratio gradually changing from 1:4 to 1:1) as the eluent, yielding a dark red solid. .

[0027] In Example 5, under nitrogen protection and in the dark, 1,8-dibromonaphthalene (429 mg, 1.5 mmol), 10-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,15-bis(3,4,5-trimethoxyphenyl)porphyrin (1.20 g, 1.95 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 87 mg, 0.075 mmol), and potassium carbonate (K2CO3, 829 mg, 6.0 mmol) were added sequentially to a 250 mL two-necked flask. After purging with nitrogen three times, a mixed solvent of degassed toluene (60 mL), ethanol (15 mL), and deionized water (15 mL) was added under a nitrogen atmosphere. The reaction mixture was heated to 85°C and refluxed with stirring at this temperature in the dark for 36 hours. After the reaction was complete, the mixture was cooled to room temperature and poured into 200 mL of ice water, then extracted with dichloromethane (3 × 100 mL). The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography using dichloromethane / petroleum ether (containing 0.5% triethylamine) as the eluent to give a purple solid 10-(8-bromonaphth-1-yl)-5,15-bis(3,4,5-trimethoxyphenyl)porphyrin. Under nitrogen protection and strict light-protection conditions, 10-(8-bromonaphth-1-yl)-5,15-bis(3,4,5-trimethoxyphenyl)porphyrin (996 mg, 1.0 mmol), 1,2-diphenylacetylene (96 mg, 0.55 mmol), palladium acetate (Pd(OAc)2) (6.7 mg, 0.03 mmol), tris(4-chlorophenyl)phosphine (P(4-ClC6H4)3) (17.1 mg, 0.045 mmol), and silver acetate (AgOAc) (200 mg, 1.2 mmol) were sequentially dissolved in anhydrous degassed 1,2-dichloroethane (DCE) (50 mL). The reaction mixture was placed in an oil bath at 85 °C and stirred under nitrogen atmosphere in the dark for 96 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered through a diatomaceous earth short column. After the filtrate was concentrated under reduced pressure, the crude product was purified by silica gel column chromatography using dichloromethane / methanol (100:1 v / v, containing 0.5% triethylamine) as the eluent to obtain a dark green solid. .

[0028] The embodiments selected in the above materials are for ease of understanding and not for limiting the process method. Those skilled in the art can easily modify the process flow or transfer it to other cases without inventive change. If these modifications also fall under the category of similar claims or similar technology of this invention, then the intent of this invention also includes these modifications.

Claims

1. A method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring, characterized in that, The synthetic route for the negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring is as follows: ； Specifically, the following steps are included: Step 1: Using the haloacenaphthene derivative shown in Formula II, a cyclization tetramerization reaction is carried out in a first organic solvent under Lewis acid catalysis to obtain a tetrabromo precursor containing a single eight-membered ring as shown in Formula III; Step 2: The tetrabromo precursor containing a single eight-membered ring, as shown in Formula III, and the disubstituted alkyne undergo a one-step multiple CH / alkyne cyclization coupling reaction in a second organic solvent in the presence of a palladium catalyst, a silver salt, and a phosphine ligand to obtain a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, as shown in Formula I.

2. The method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring according to claim 1, characterized in that, In the first step, the Lewis acid is titanium tetrachloride (TiCl4), the first organic solvent is o-dichlorobenzene, and the reaction temperature of the cyclization tetramerization reaction is 150-200℃.

3. The method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring according to claim 1, characterized in that, In the first step, 240-250 parts by mass of haloacenaphthene derivative, 0.6-0.8 parts of Lewis acid, and 20-40 parts of first organic solvent are prepared.

4. The method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring according to claim 1, characterized in that, In the second step, the following proportions are made by mass: 40-60 parts of a tetrabromo precursor containing a single eight-membered ring, 60-70 parts of a disubstituted alkyne, 1-2 parts of a palladium catalyst, 40-50 parts of a silver salt, 2-3 parts of a phosphine ligand, and 10-20 parts of a second organic solvent.

5. The method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring according to claim 1, characterized in that, In the second step, the palladium catalyst is palladium acetate Pd(OAc)2, the silver salt is silver acetate AgOAc, and the phosphine ligand is tris(4-chlorophenyl)phosphine P(4-ClC6H4)3.

6. The method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring according to claim 1, characterized in that, In the second step, the second organic solvent is 1,2-dichloroethane, and the reaction temperature is 70-90℃.

7. The method for synthesizing negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring according to claim 1, characterized in that, In the second step, the disubstituted alkyne is 1,2-diarylacetylene, wherein the aryl group in the 1,2-diarylacetylene is selected from phenyl, substituted phenyl, or naphthyl.

8. A negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, prepared by the synthetic method according to any one of claims 1-7, characterized in that, The negative curvature polycyclic aromatic hydrocarbons containing an eight-membered ring are shown in general formula (Ⅰ): Formula (Ⅰ), wherein R is a substituted aryl group containing C1-C12 alkyl, C1-C12 alkoxy, trifluoromethyl, silyl, amino or halogen.

9. The application of a negative curvature polycyclic aromatic hydrocarbon containing an eight-membered ring, prepared by any one of the synthesis methods described in claims 1-7, in the preparation of optoelectronic devices.

10. The application according to claim 9, characterized in that: The optoelectronic device is a perovskite solar cell, and the negative curvature polycyclic aromatic hydrocarbon exists as an additive in the perovskite active layer.

Images