Seven-membered ring-containing long acenes and methods for their preparation

Abstract

The application provides a long acene derivative molecule containing a seven-membered ring and a preparation method thereof. The structure is shown in formula I, formula II or formula III. The application takes a cycloaddition reaction, a double coupling reaction and other reactions as key steps, and long acene derivative molecules containing a seven-membered ring shown in formula I, formula II and formula III are simply and efficiently synthesized. The method has the advantages of high efficiency and simplicity, short synthesis period, macro preparation of raw materials, synthesis of novel non-benzene polycyclic aromatic hydrocarbons containing a seven-membered ring which cannot be obtained by traditional methods and the like. The novel non-benzene polycyclic aromatic hydrocarbons containing a seven-membered ring synthesized by the application have unique optical physical and electrochemical properties and good photoelectric functions.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis and optoelectronic materials, specifically relating to long benzoxene derivative molecules containing seven-membered rings and their preparation methods. Background Technology

[0002] Benzene compounds, as a prominent class of organic functional materials, show potential applications in various fields such as organic semiconductors and organic light-emitting materials. Typically, these compounds exhibit a planar configuration, but the introduction of non-benzene ring systems, such as negatively curved seven-membered rings, results in a wavy, curved structure. As the length of the Benzene ring increases, its stability decreases significantly; however, introducing a seven-membered ring into the Benzene structure not only maintains high transport capacity but also effectively improves stability. The methods for introducing seven-membered rings into polycyclic aromatic hydrocarbons (PAHs) are limited, which severely restricts the development of seven-membered PAH compounds. Benzene compounds containing seven-membered rings can serve as an important platform for studying the influence of the seven-membered ring on structure and properties. By combining the unique optoelectronic properties of the seven-membered ring with the Benzene skeleton, we can explore the effects of the seven-membered ring introduction on the stability, solubility, molecular configuration, aromaticity, electronic configuration, and redox properties of Benzene molecules. This holds promise for obtaining high-performance novel semiconductor materials and achieving the regulation of the structure and properties of these Benzene derivatives.

[0003] By introducing a seven-membered ring into the framework of the star semiconductor benzo[a]benzene, we designed and synthesized benzo[a]benzene derivatives containing a seven-membered ring. Benzene compounds, as important organic functional materials, have broad potential applications in various fields. Combining the unique photoelectric properties of the seven-membered ring with the benzo[a]benzene framework, we conducted in-depth research on the effects of the introduction of the seven-membered ring on the stability, molecular configuration, electronic configuration, and redox properties of benzo[a]benzene molecules. This research holds promise for developing high-performance novel semiconductor materials and may enable precise control over the structure and properties of these benzo[a]benzene derivatives.

[0004] Furthermore, the synthesis of polycyclic aromatic hydrocarbons containing seven-membered rings is quite difficult, which greatly limits the development of such materials. Therefore, establishing a new, concise, efficient, and large-scale bottom-up method for synthesizing long benzo[a]benzene derivatives containing seven-membered rings is of great significance for expanding the types of organic semiconductors and helping us to better understand the relationship between the molecular structure and properties of long benzo[a]benzene derivatives containing seven-membered rings.

[0005] References: JEAnthony, The larger acenes: versatile organicsemiconductors, Angew Chem Int Ed Engl, 2008, 47, 452-483. W. Chen, F. Yu, Q. Xu, G. Zhou and Q. Zhang, Recent Progress in High Linearly Fused Polycyclic Conjugated Hydrocarbons (PCHs, n>6) with Well-Defined Structures,AdvSci(Weinh),2020,7,1903766. Summary of the Invention

[0006] The purpose of this invention is to provide a long benzoxene derivative molecule containing a seven-membered ring and its preparation method.

[0007] The long benzoxene derivative molecule containing a seven-membered ring provided by this invention has the structure shown in Formula I, Formula II or Formula III:

[0008]

[0009] In Formula I above, R1 is independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, nitro, ester, carboxyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain alkyl or branched-chain alkyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched-chain alkoxy, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched-chain alkylamino, trimethylsilyl (TMS), triisopropylsilyl (TIPS), tert-butyldimethylsilyl (TBDMS), substituted or unsubstituted phenyl; specifically, it can be any one of H or bromine;

[0010] In Formula II above, R2 is independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, nitro, ester, carboxyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain alkyl or branched alkyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4 (e.g., tert-butyl)) straight-chain or branched alkoxy, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched alkylamino, trimethylsilyl (TMS), triisopropylsilyl (TIPS), tert-butyldimethylsilyl (TBDMS), substituted or unsubstituted phenyl.

[0011] In Formula III above, R3 is independently selected from any one of hydrogen, substituted or unsubstituted phenyl, C4-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain alkyl or branched alkyl, C4-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched alkoxy, C4-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched alkylamino, trimethylsilyl (TMS), triisopropylsilyl (TIPS), and tert-butyldimethylsilyl (TBDMS);

[0012] The substituents in the substituted phenyl groups are each independently selected from: fluorine, chlorine, bromine, iodine, nitro, ester, carboxyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain alkyl or branched alkyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4 (e.g., tert-butyl)) straight-chain or branched alkoxy, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched alkylamino, trimethylsilyl (TMS), triisopropylsilyl (TIPS), tert-butyldimethylsilyl (TBDMS), any one of the following.

[0013] The present invention also provides a method for preparing the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula I above.

[0014] The long benzoxene derivative molecule containing a seven-membered ring shown in Formula I above was prepared by a method including the following steps: in the presence of salt, in a solvent, compound (1) and compound (2) undergo a [4+2] cycloaddition reaction to obtain the long benzoxene derivative molecule containing a seven-membered ring shown in Formula I;

[0015]

[0016] The definition of R1 in compound (2) is the same as the definition of R1 in formula I.

[0017] The specific operation is as follows: First, place compounds (1) and (2) in a reaction vessel, add salt and solvent, stir and heat the reaction system for a period of time, and then perform post-treatment on the reaction system to obtain the target product, a long benzoxene derivative molecule containing a seven-membered ring as shown in Formula I.

[0018] The molar ratio of compound (1) to compound (2) can be 1:2-10, specifically 1:4;

[0019] The salt may be sodium iodide or potassium iodide, preferably sodium iodide or potassium iodide;

[0020] The molar ratio of compound (1) to salt can be 1:0.1-10, specifically 1:8;

[0021] The solvent may be at least one of tetrahydrofuran, N,N-dimethylformamide, and toluene, preferably N,N-dimethylformamide;

[0022] The reaction temperature can be 25℃-120℃, preferably 65℃.

[0023] The reaction system can be stirred and heated for 24-72 hours, preferably 48 hours.

[0024] The reaction is carried out in an atmosphere of air, nitrogen, or argon.

[0025] After the reaction is completed, the following post-processing operations are also included: After the reaction is completed, a saturated sodium thiosulfate solution is added, the reaction system is extracted with ethyl acetate, the organic phase is collected, the solvent is removed from the organic phase by rotary evaporation, and then the organic phase is separated and purified by column chromatography, wherein petroleum ether / dichloromethane (volume ratio 10:1-2:1) is used as the eluent to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula I.

[0026] The present invention also provides a method for preparing the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula II above.

[0027] The long benzo[3]benzene derivative molecule containing a seven-membered ring shown in Formula II above was prepared by a method including the following steps: in an inert atmosphere, in the presence of a catalyst, a base and a ligand, compound (3) and compound (4) underwent a bicoupling reaction to obtain the long benzo[3]benzene derivative molecule containing a seven-membered ring shown in Formula II.

[0028]

[0029] In compound 3, the definition of R2 is the same as that in formula II. 4 It is independently selected from borate group and borate pinacol ester group.

[0030] The specific preparation method includes the following steps:

[0031] First, place compound (3), catalyst, base, ligand and compound (4) in a reaction vessel, replace the reaction atmosphere with nitrogen or argon, add reaction solvent, stir and heat the reaction system for a period of time, and then perform post-treatment on the reaction system to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula II.

[0032] The catalyst may be selected from at least one of bis(dibenzylacetone)palladium, palladium acetate, palladium acetate, ferrocene diphenylphosphine palladium dichloride, tetratriphenylphosphine palladium, dichloroditriphenylphosphine palladium, trifluoroacetate palladium, allyl palladium(II) chloride dimer, bis(tri-tert-butylphosphine)palladium and di-μ-chlorobis[5-chloro-2-[(4-chlorophenyl)(oxime)methyl]phenyl]palladium(II) dimer, specifically bis(dibenzylacetone)palladium;

[0033] The alkali may be at least one of potassium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, and cesium carbonate, preferably cesium carbonate;

[0034] The ligand may be selected from at least one of the following: tris[3,5-di(trifluoromethyl)phenyl]phosphine, 2-(dicyclohexylphosphine)biphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, tris(o-methylphenyl)phosphine, tris(p-phenylmethylphosphine) and tris(2,6-dimethoxyphenyl)phosphine, 1,4-bis(diphenylphosphine)butane, 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 2-(dicyclohexylphosphine)-2'-(N,N-dimethylamine)biphenyl and 1,5-bis(diphenylphosphine)pentane, preferably 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl;

[0035] The reaction solvent may be a mixture of at least one of tetrahydrofuran, N,N-dimethylformamide, and toluene with water, preferably a mixture of toluene and water; the preferred mixing ratio is toluene to water volume ratio of 4:1.

[0036] The reaction temperature can be 25℃-120℃, preferably 110℃;

[0037] The reaction system can be stirred and heated for 24-72 hours, preferably 48 hours.

[0038] The reaction is carried out under a nitrogen or argon atmosphere;

[0039] The molar ratio of compound (4) and compound (3), catalyst, base and ligand can be 1:2.0-4.0:0.05-1.0:2.0-4.0:0.1-2.0, specifically 1:2.2:0.5:3.0:1.0;

[0040] After the reaction is completed, the following post-processing operation is also included: after the reaction is completed, the solvent is removed by rotary evaporator, and then the system is separated and purified by column chromatography, wherein petroleum ether / dichloromethane (volume ratio 4:1) is used as the eluent to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula II.

[0041] The present invention also provides a method for preparing the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula III above.

[0042] The long benzoxene derivative molecule containing a seven-membered ring shown in Formula III above is prepared by a method including the following steps:

[0043] 1) In an inert atmosphere and in the presence of a lithium reagent, compound (4) and compound (5) undergo a [4+2] cycloaddition reaction to obtain compound (6);

[0044]

[0045] The definition of R3 in compound 5 is the same as the definition of R3 in formula III;

[0046] The definition of R3 in compound 6 is the same as the definition of R3 in formula III;

[0047] 2) In an inert atmosphere, in the presence of metal and acid, compound 6 undergoes a reduction reaction to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula III.

[0048] The specific operation of step 1) of the above method is as follows:

[0049] First, place compound (5) and compound (4) in a reaction vessel, replace the reaction atmosphere with nitrogen or argon, add the reaction solvent, stir and lower the temperature of the reaction system to below 0℃, add lithium reagent and stir for 0.5-1h, then stop cooling, restore to room temperature, stir for 6-12h, and then perform post-treatment on the reaction system to obtain compound (6).

[0050] The molar ratio of compound (4) to compound (5) can be 1:2.2-3, specifically 1:2.2;

[0051] The lithium reagent may be at least one of n-butyllithium and tert-butyllithium;

[0052] The molar ratio of compound (4) to the lithium reagent can be 1:2-4.8, specifically 1:4.8;

[0053] The reaction solvent may specifically be toluene;

[0054] The specific steps of the post-processing are as follows: quench the reaction system with saturated brine, extract the organic phase with dichloromethane, separate the product by column chromatography, and obtain the crude product of compound (6).

[0055] The specific operation of step 2) of the above method is as follows: place compound (6) and metal in a reaction vessel, replace the reaction atmosphere with nitrogen or argon, add reaction solvent and acid in sequence, stir and heat the reaction system for 12-48 hours, and then perform post-treatment on the reaction system to obtain the product.

[0056] The metal may be at least one of zinc and magnesium;

[0057] The acid may be at least one of acetic acid and hydrochloric acid;

[0058] The molar ratio of compound (6) to metal can be 1:2-20, specifically 1:10;

[0059] The reaction solvent may specifically be toluene;

[0060] The reaction temperature is 30-110℃, specifically 110℃; the reaction time is 10-20h, specifically 12h.

[0061] The specific steps of the post-processing are as follows: quench the reaction system with saturated brine, extract the organic phase with dichloromethane, and separate the product by column chromatography, wherein petroleum ether / dichloromethane (volume ratio 5:1) is used as the eluent to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula III.

[0062] The application of the long benzo[a]benzene derivative molecules containing a seven-membered ring as shown in Formula I, Formula II or Formula III above in the preparation of organic semiconductor materials is also within the scope of protection of this invention.

[0063] This invention synthesizes long benzo[a]benzene derivatives containing seven-membered rings as shown in Formulas I, II, and III using the above-described preparation method. The crystal structures of these molecules were characterized by single-crystal X-ray diffraction (XRD). The spectral properties of solutions containing these molecules were tested using UV-Vis and fluorescence spectroscopy. The electrochemical properties of these molecules were characterized by cyclic voltammetry. The preparation of the molecule shown in Formula I utilizes a key [4+2] cycloaddition reaction. The preparation of the molecule shown in Formula II utilizes a bicoupling cyclization strategy. The preparation of the molecule shown in Formula III utilizes the [4+2] cycloaddition and reduction reactions of benzoyne. This invention provides a concise and efficient synthesis of long benzo[a]benzene derivatives containing seven-membered rings as shown in Formulas I, II, and III. This method has advantages such as high efficiency and simplicity, short synthesis cycle, large-scale preparation of raw materials, and the ability to synthesize novel non-benzene polycyclic aromatic hydrocarbons containing seven-membered rings that cannot be obtained by traditional methods. The novel non-benzene polycyclic aromatic hydrocarbons containing a seven-membered ring synthesized by this invention possess unique photophysical and electrochemical properties and exhibit excellent photoelectric functionality. Attached Figure Description

[0064] Figure 1 The synthetic route is shown in Formula I of Example 1.

[0065] Figure 2 This is the synthetic route for the molecule shown in Formula II in Example 2.

[0066] Figure 3 The synthetic route for the molecule shown in Formula III in Example 3 is shown below.

[0067] Figure 4 The molecule (R) shown in Formula I in Example 1 1 It has a crystal structure of H).

[0068] Figure 5 The crystal structure of the molecule shown in Formula II in Example 2 is shown.

[0069] Figure 6 The eutectic is a molecule (R1 is H) of the formula shown in Example 6 with a molecule-to-C60 ratio of 1:1.

[0070] Figure 7 The eutectic is the molecule shown in Formula I in Example 6 (R1 is H):C60 molecule ratio of 1:3.

[0071] Figure 8 Cyclic voltammetry curves are shown for the molecule represented by Formula I in Example 1 (R1 is H), the molecule represented by Formula II in Example 2, and the molecule represented by Formula III in Example 3.

[0072] Figure 9 Solution absorption and emission spectra characterized the molecules shown in Formula I of Example 1 (R1 is H), the molecules shown in Formula II of Example 2, and the molecules shown in Formula III of Example 3. Detailed Implementation

[0073] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0074] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0075] Example 1: Synthesis of the molecule shown in Formula I (R1 is hydrogen or bromine)

[0076] Chemical reaction flow chart as follows Figure 1 As shown, the compound (1) used in Example 1 was synthesized by a method reported in the literature (Angew. Chem. Int. Ed. 2020, 59, 3529–3533).

[0077] The specific reaction steps and conditions are as follows:

[0078] In a Schlenk tube equipped with a magnetic stirrer, compound (1) (1 equivalent), compound (2) (4 equivalent), and sodium iodide (8 equivalent) were added. The air in the container was replaced with nitrogen using the Schlenk technique. Subsequently, under a nitrogen atmosphere, 8 mL of ultra-dry N,N-dimethylformamide was added. The reaction system was stirred and heated at 65 °C for 48 h. In the post-treatment stage, the reaction system was treated with a saturated sodium thiosulfate aqueous solution, extracted with ethyl acetate, and the organic phase was collected and evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was separated by silica gel column chromatography (volume ratio of petroleum ether: dichloromethane = 10:1-2:1) to obtain the molecule shown in Formula I, where R1 is hydrogen or bromine. The obtained products were all yellow solid powders. The molecule shown in Formula I was characterized by single-crystal diffraction and high-resolution mass spectrometry. HR-MS (MALDI-FTICR): m / z calcd. for C46H26([M]+): 578.2029, found: 578.2027.

[0079] Example 2: Synthesis of the molecule shown in Formula II (R2 is tert-butyl, R...) 4 (boronic acid group)

[0080] Chemical reaction flow chart as follows Figure 2 As shown, the molecule represented by Formula I in Example 1 (R1 is bromine) is required. The specific reaction conditions are as follows:

[0081] In a Schlenk tube equipped with a magnetic stirrer, the molecule shown in Formula I (1 equivalent), compound (3) (2.2 equivalents), bis(dibenzylacetone)palladium (0.5 equivalents), cesium carbonate (3 equivalents), and 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (1 equivalent) were added. The air in the container was replaced with nitrogen using the Schlenk technique. Subsequently, under a nitrogen atmosphere, 4 mL of toluene and 1 mL of water were added. The reaction system was stirred and heated to 110 °C for 48 h.

[0082] After the reaction, the solvent was removed by rotary evaporation, followed by separation and purification by column chromatography using petroleum ether / dichloromethane (volume ratio 4:1) as the eluent. This yielded molecule II (R2 being tert-butyl), an orange-yellow solid powder. The molecule represented by Formula II was characterized by single-crystal diffraction and high-resolution mass spectrometry. HR-MS (MALDI-FTICR): m / z calcd. for C86H70([M]+): 1102.5472, found: 1102.5479.

[0083] Example 3: Synthesis of the molecule shown in Formula III (R3 is phenyl)

[0084] Chemical reaction flow chart as follows Figure 3As shown, the molecule represented by Formula I in Example 1 (R1 is bromine) is required. The specific reaction conditions are as follows:

[0085] In a Schlenk tube equipped with a magnetic stirrer, the molecule shown in Formula I (1 equivalent) and compound (5) (2.2 equivalent) were added. The air in the container was replaced with nitrogen using the Schlenk technique. 4 mL of toluene was added, the mixture was stirred, and the reaction temperature was lowered to -78 °C. An n-BuLi solution (4.8 equivalent, the volume can be calculated based on the molar concentration) was added dropwise, and the mixture was stirred for 1 h. Then, the mixture was stirred at room temperature (approximately 25 °C) for 12 h. In the post-treatment stage, the reaction system was treated with a saturated sodium chloride aqueous solution, extracted with dichloromethane, and the organic phase was collected and evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product (petroleum ether: dichloromethane = 5:1) was separated by silica gel column chromatography and evaporated to dryness to obtain the crude product of compound (6), which was a yellow solid powder.

[0086] In a Schlenk tube equipped with a magnetic stirrer, all the crude product of compound (6) from the previous step and zinc powder (10 equivalents) were added. The air in the container was replaced with nitrogen using the Schlenk technique. Several milliliters of a 1:1 mixture of toluene and acetic acid were added, the amount of which should be greater than the amount needed to completely dissolve the organic solid. The mixture was stirred and heated to 110°C for 12 hours. The reaction system was quenched with saturated brine. The organic phase was extracted with dichloromethane, and the product was separated by column chromatography. Petroleum ether / dichloromethane (volume ratio 5:1) was used as the eluent to obtain the molecule shown in Formula III, which is an orange-yellow solid powder. The molecule shown in Formula III was characterized by high-resolution mass spectrometry. HR-MS (MALDI-FTICR): m / z calcd. for C86H50([M]+): 1082.3907, found: 1082.3917.

[0087] Example 4: Preparation of crystals of the molecule shown in Formula I (R1 is hydrogen)

[0088] The molecule (R) of Formula I obtained in Example 1 of this invention 1 Methanol (R1 being hydrogen) is obtained by slowly diffusing methanol into a chloroform solution from a dichloromethane solution via solvent diffusion. The crystal structure was determined using a single-crystal diffractometer. The crystal structure of the molecule (R1 being hydrogen) shown in Formula I of this invention is as follows: Figure 4 As shown, the introduction of the seven-membered ring causes the benzene skeleton to bend, resulting in a bent molecular structure. Its characteristic feature is that, within the unit cell, the molecule represented by Formula I exists as a pair of enantiomers, P,P and M,M.

[0089] Example 5: Preparation of crystals of the molecule shown in Formula II

[0090] The molecule of formula II obtained in Example 2 of this invention was dissolved in a toluene solution, and methanol was slowly diffused into the toluene solution via solvent diffusion. The crystal structure was determined by single-crystal diffraction. The crystal structure of the molecule of formula II of this invention is as follows: Figure 5 As shown, the introduction of the seven-membered ring causes the benzene skeleton to bend, resulting in a bent molecular structure. Its characteristic feature is that, within the unit cell, the molecule shown in Formula II exists as a pair of enantiomers, P,P and M,M.

[0091] Example 6: Preparation of two eutectic crystals of the molecule shown in Formula I (R1 is H) and the C60 molecule:

[0092] By changing the culture conditions, specifically by changing the molar ratio of the molecule shown in Formula I (R1 is H) to the C60 molecule, two different ratios of eutectic crystals of the molecule shown in Formula I (R1 is H) and the C60 molecule can be cultured (1:1 and 1:3, respectively).

[0093] The eutectic cultivation method for the molecule shown in Formula I (R1 is H):C60 molecules in a 1:1 ratio is as follows: The molecule shown in Formula I (R1 is H) and C60 molecules are completely dissolved in chlorobenzene solution at a molar ratio of 2:1. The amount of chlorobenzene solution used is just enough to dissolve the solid substance. The solution is left to stand in a cool, dry place to evaporate naturally until black crystals grow. The crystal structure is determined by a single-crystal diffractometer. The crystal structure of the eutectic is as follows: Figure 6 As shown, the molecule represented by Formula I (R) 1 The curved portion of the molecule (where R1 is H) can accommodate one C60 molecule. In the eutectic, the ratio of the molecule shown in Formula I (where R1 is H) to the C60 molecule is 1:1, and the ratio of the enantiomers of P,P and M,M in the molecule shown in Formula I (where R1 is H) is 1:1.

[0094] The eutectic cultivation method for the molecule shown in Formula I (R1 is H):C60 molecules in a 1:3 ratio is as follows: The molecule shown in Formula I (R1 is H) and C60 molecules are completely dissolved in chlorobenzene solution at a molar ratio of 1:2. The amount of chlorobenzene solution used is just enough to dissolve the solid substance. The solution is left to stand in a cool, dry place to evaporate naturally until black crystals grow. The crystal structure is determined by single-crystal diffraction. The crystal structure of the eutectic is as follows. Figure 7 As shown, the characteristic is that the curved portion of the molecule shown in Formula I (R1 is H) can accommodate one C60 molecule, and in addition, there is a layered structure composed entirely of C60 molecules. In the eutectic, the ratio of the molecule shown in Formula I (R1 is H) to the C60 molecule is 1:3, and the molecule shown in Formula I (R1 is H) has a C60 molecule ratio of 1:3. 1 The enantiomer ratio of P,P and M,M in H is 1:1.

[0095] Example 7: Electrochemical properties and frontier orbital levels (HOMO and LUMO) of the molecules shown in Formula I (R1 is H), Formula II, and Formula III were measured using electrochemical cyclic voltammetry:

[0096] The electrochemical properties of the molecules shown in Formula I (R1 is H) in Example 1, Formula II in Example 2, and Formula III in Example 3 of this invention were tested using an electrochemical workstation. Ferrocene was used as the standard, tetrabutylammonium hexafluorophosphate was used as the electrolyte, and the electrolyte solution was dichloromethane (0.1 M concentration) containing tetrabutylammonium hexafluorophosphate. A standard three-electrode system was used for testing, with a glassy carbon electrode as the working electrode and platinum wire as the counter electrode. The Ag / Ag ratio was [not specified in the original text]. + As a reference electrode, its cyclic voltammetry curve was measured as follows: Figure 8 As shown, from Figure 8 It can be seen that: the molecule shown in Equation I (R1 is H) has one quasi-reversible reduction peak and four irreversible oxidation peaks, with the reduction peak at -2.10 V and the oxidation peaks at 0.45 V, 0.86 V, 1.21 V, and 1.33 V. The calculated HOMO and LUMO energy levels are -5.18 eV and -2.81 eV, respectively; the molecule shown in Equation II has one quasi-reversible reduction peak and three irreversible oxidation peaks, with the reduction peak at -2.05 V and the oxidation peaks at -2.05 V. The oxidation peaks are at 0.45V, 0.91V, and 1.27V, and the calculated HOMO and LUMO energy levels are -5.19eV and -2.86eV, respectively. The molecule shown in Equation III has one reversible reduction peak and three irreversible oxidation peaks. The reduction peak is at -1.94V, and the oxidation peaks are at 0.45V, 0.74V, and 0.96V. The calculated HOMO and LUMO energy levels are -5.18eV and -3.0eV, respectively.

[0097] Example 8: Solution absorption and emission spectra characterization of the molecules shown in Formula I (R1 is H), Formula II, and Formula III.

[0098] The molecule shown in Formula I of Example 1 (R1 is H), the molecule shown in Formula II of Example 2, and the molecule shown in Formula III of Example 3 were dissolved in toluene solvent (concentration of 10). -5 The absorption spectra of the molecule shown in Formula I in Example 1 (R1 is H), the molecule shown in Formula II in Example 2, and the molecule shown in Formula III in Example 3 in solution were measured as follows: Figure 9 As shown.

[0099] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. A long benzoxene derivative molecule containing a seven-membered ring, the structure of which is shown in Formula I, Formula II or Formula III: In Formula I, R1 is independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, nitro, ester, carboxyl, C1-C18 straight-chain alkyl or branched alkyl, C1-C18 straight-chain or branched alkoxy, C1-C18 straight-chain or branched alkylamino, trimethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, substituted or unsubstituted phenyl; R2 is independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, nitro, ester, carboxyl, C1-C18 straight-chain or branched alkyl, C1-C18 straight-chain or branched alkoxy, C1-C18 straight-chain or branched alkylamino, trimethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, substituted or unsubstituted phenyl. In Formula III, R3 is independently selected from any one of hydrogen, substituted or unsubstituted phenyl, C4-C18 straight-chain alkyl or branched alkyl, C4-C18 straight-chain or branched alkoxy, C4-C18 straight-chain or branched alkylamino, trimethylsilyl, triisopropylsilyl, and tert-butyldimethylsilyl. in, The substituents in the substituted phenyl group are each independently selected from any one of the following: fluorine, chlorine, bromine, iodine, nitro, ester, carboxyl, C1-C18 straight-chain alkyl or branched alkyl, C1-C18 straight-chain or branched alkoxy, C1-C18 straight-chain or branched alkylamino, trimethylsilyl, triisopropylsilyl, and tert-butyldimethylsilyl.

2. A method for preparing the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula I of claim 1, comprising the following steps: in the presence of a salt, in a solvent, causing compound (1) to undergo a [4+2] cycloaddition reaction with compound (2) to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula I; The definition of R1 in compound (2) is the same as the definition of R1 in formula I.

3. The method according to claim 2, characterized in that, The operation is as follows: First, place compounds (1) and (2) in a reaction vessel, add salt and solvent, stir and heat the reaction system for a period of time, and then perform post-treatment on the reaction system to obtain the target product, a long benzoxene derivative molecule containing a seven-membered ring as shown in Formula I. The molar ratio of compound (1) to compound (2) is 1:2-10; The salt is sodium iodide or potassium iodide; The molar ratio of compound (1) to salt is 1:0.1-10; The reaction temperature is 25℃-120℃; The reaction system was stirred and heated for 24-72 hours.

4. A method for preparing the long benzo[a]benzene derivative molecule containing a seven-membered ring as shown in Formula II of claim 1, comprising the following steps: in an inert atmosphere, in the presence of a catalyst, a base and a ligand, causing compound (3) and compound (4) to undergo a bicoupling reaction to obtain the long benzo[a]benzene derivative molecule containing a seven-membered ring as shown in Formula II. In compound 3, R2 is defined in the same way as R2 in formula II, and R4 is independently selected from borate group and borate pinacol ester group.

5. The method according to claim 4, characterized in that, The operation is as follows: First, place compound (3), catalyst, base, ligand and compound (4) in a reaction vessel, replace the reaction atmosphere with nitrogen or argon, add reaction solvent, stir and heat the reaction system for a period of time, and then perform post-treatment on the reaction system to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula II. The catalyst is selected from at least one of bis(dibenzylacetone)palladium, palladium acetate, ferrocene diphenylphosphine palladium dichloride, tetratriphenylphosphine palladium, dichloroditriphenylphosphine palladium, trifluoroacetic acid palladium, allyl palladium(II) chloride dimer, bis(tri-tert-butylphosphine)palladium and di-μ-chlorobis[5-chloro-2-[(4-chlorophenyl)(oxime)methyl]phenyl]palladium(II) dimer; The alkali is at least one of potassium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, and cesium carbonate; The ligand is selected from at least one of the following: tris[3,5-di(trifluoromethyl)phenyl]phosphine, 2-(dicyclohexylphosphine)biphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, tris(o-methylphenyl)phosphine, tris(p-phenylmethylphosphine) and tris(2,6-dimethoxyphenyl)phosphine, 1,4-bis(diphenylphosphine)butane, 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 2-(dicyclohexylphosphine)-2'-(N,N-dimethylamine)biphenyl and 1,5-bis(diphenylphosphine)pentane; The reaction temperature is 25℃-120℃; The reaction system is stirred and heated for 24-72 hours. The molar ratios of compound (4) and compound (3), catalyst, base and ligand are as follows: 1:2.0-4.0:0.05-1.0:2.0-4.0:0.1-2.

0.

6. A method for preparing the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula III of claim 1, comprising the following steps: 1) In an inert atmosphere and in the presence of a lithium reagent, compound (4) and compound (5) undergo a [4+2] cycloaddition reaction to obtain compound (6); The definition of R3 in compound 5 is the same as the definition of R3 in formula III; The definition of R3 in compound 6 is the same as the definition of R3 in formula III; 2) In an inert atmosphere, in the presence of metal and acid, compound 6 undergoes a reduction reaction to obtain the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula III.

7. The method according to claim 6, characterized in that, Step 1) is as follows: First, place compound (5) and compound (4) in a reaction vessel, replace the reaction atmosphere with nitrogen or argon, add the reaction solvent, stir and lower the temperature of the reaction system to below 0℃, add lithium reagent and stir for 0.5-1h, then stop cooling, restore to room temperature, stir for 6-12h, and then perform post-treatment on the reaction system to obtain compound (6). The molar ratio of compound (4) to compound (5) is 1:2.2-3; The lithium reagent may be at least one of n-butyllithium and tert-butyllithium; The molar ratio of compound (4) to the lithium reagent is 1:2-4.8; The specific operation of step 2) is as follows: place compound (6) and metal in a reaction vessel, replace the reaction atmosphere with nitrogen or argon, add reaction solvent and acid in sequence, stir and heat the reaction system for 12-48 hours, and then perform post-treatment on the reaction system to obtain the product. The metal is at least one of zinc and magnesium; The acid is at least one of acetic acid and hydrochloric acid; The molar ratio of compound (6) to the metal is 1:2-20; The reaction temperature is 30-110℃.

8. The application of the long benzoxene derivative molecule containing a seven-membered ring as shown in Formula I, Formula II or Formula III of claim 1 in the preparation of organic semiconductor materials.

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