Helical chiral polycyclic aromatic hydrocarbon compounds, open-shell compounds, and preparation methods and applications thereof

Abstract

This application relates to the field of materials and provides a helical chiral polycyclic aromatic hydrocarbon compound, an open-shell compound, and methods for their preparation and application. The helical chiral polycyclic aromatic hydrocarbon compound has the general structural formula shown in Formula I: #imgabs0#; wherein R is selected from the following structures: #imgabs1#, #imgabs2#. The helical chiral polycyclic aromatic hydrocarbon compound of this application possesses unique electronic and optical properties, particularly narrowband emission. Its luminescence spectrum has a narrow full width at half maximum (FWHM), reaching 11 to 17 nm. It is suitable for applications in chemical sensors, optoelectronic devices, and biomedicine.

Description

Technical Field

[0001] The present application relates to the field of materials, and in particular to a helical chiral polycyclic aromatic hydrocarbon compound, an open-shell compound, and a preparation method and application thereof. Background Art

[0002] Polycyclic aromatic hydrocarbons (PAHs) are organic compounds composed of multiple benzene rings connected by shared carbon atoms. Helical PAHs exhibit a helical molecular configuration, which imparts them with a range of exceptional physicochemical properties, including high optical rotation, circular dichroism, and unique optical responses.

[0003] Polycyclic aromatic hydrocarbons with helical chirality have great application potential in optoelectronic materials, but how to optimize the optical and electrical properties of such compounds remains a huge challenge. Summary of the Invention

[0004] In response to the above-mentioned deficiencies in the prior art, the purpose of this application is to provide a helical chiral polycyclic aromatic hydrocarbon compound, an open-shell compound, and a preparation method and application thereof. The helical chiral polycyclic aromatic hydrocarbon compound has unique electronic and optical properties, especially narrow-band emission characteristics, and the full width at half maximum (FWHM) of the luminescence spectrum is relatively narrow, reaching 11nm~17nm. Such compounds can be used in chemical sensors, optoelectronic devices, biomedicine and other fields.

[0005] To achieve the above-mentioned invention objectives, the technical solutions adopted in this application are as follows:

[0006] In the first aspect, the embodiments of the present application provide a helical chiral polycyclic aromatic hydrocarbon compound, the general structural formula of which is shown in Formula I:

[0007] ; wherein R is selected from the following structures: 、 .

[0008] In a second aspect, the present invention further provides a method for preparing the helical chiral polycyclic aromatic hydrocarbon compound of the first aspect, comprising the following steps:

[0009] ;

[0010] Wherein, R is selected from the following structures: 、 ;

[0011] Synthesis of compound IV:

[0012] Compound II reacts with compound III in a first solvent in the presence of a first base and a first catalyst to obtain compound IV;

[0013] Synthesis of compound Ⅰ:

[0014] The compound IV is dissolved in a second solvent to obtain a first solution, and then a ferric chloride solution is added dropwise to the first solution, and the mixture is stirred and reacted at a first temperature to obtain compound I.

[0015] In a third aspect, an embodiment of the present application further provides an open-shell compound, which is prepared from the helical chiral polycyclic aromatic hydrocarbon compound of the first aspect by chemical oxidation.

[0016] In a fourth aspect, the present invention further provides a method for preparing the open-shell compound of the third aspect, comprising the following steps:

[0017] ;

[0018] Synthesis of compound XV:

[0019] Under nitrogen atmosphere, compound I is dissolved in the tenth solvent, and n-butyl lithium is added dropwise to generate compound XV in situ;

[0020] Synthesis of compound XIV:

[0021] Iodine is added to the compound XV to generate compound XIV in situ.

[0022] In a fifth aspect, the embodiments of the present application also provide the use of the helical chiral polycyclic aromatic hydrocarbon compound of the first aspect, or the open-shell compound of the third aspect in the preparation of chemical sensors (for example, gas sensors and biosensors), optoelectronic devices (for example, field-effect transistors, photodetectors, organic light-emitting diodes, solar cells, spintronic devices, etc.).

[0023] The beneficial effects of the present application include at least: the helical chiral polycyclic aromatic hydrocarbon compound provided in the embodiments of the present application has unique electronic and optical properties, especially narrow-band emission characteristics, and the full width at half maximum (FWHM) of its luminescence spectrum is relatively narrow, reaching 11nm~17nm, and can be applied to chemical sensors, optoelectronic devices, biomedicine and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments or descriptions of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0025] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of compound 1 prepared in Example 1 of the present application;

[0026] Figure 2 This is a high-resolution mass spectrum of compound 1 prepared in Example 1 of the present application;

[0027] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of compound 2 prepared in Example 1 of the present application;

[0028] Figure 4 This is a high-resolution mass spectrum of compound 2 prepared in Example 1 of the present application;

[0029] Figure 5 is the absorption spectrum of compound 1 prepared in Example 1 of the present application in different solvents;

[0030] Figure 6 1 is the emission spectrum of compound 1 prepared in Example 1 of the present application in different solvents;

[0031] Figure 7 is the circular dichroism spectrum of compound 1 prepared in Example 1 of the present application;

[0032] Figure 8 is the absorption spectrum of compound 2 prepared in Example 1 of the present application in different solvents;

[0033] Figure 9 1 is the emission spectrum of compound 2 prepared in Example 1 of the present application in different solvents;

[0034] Figure 10 is the circular dichroism spectrum of compound 2 prepared in Example 1 of the present application;

[0035] Figure 11 The UV-visible-near-infrared absorption spectra of compound 1 prepared in Example 1 of the present application, and compounds XV-1 and XIV-1 prepared in Example 2;

[0036] Figure 12 This is the EPR spectrum of compound XIV-1 prepared in Example 2 of the present application;

[0037] Figure 13 The UV-visible-near-infrared absorption spectra of compound 2 prepared in Example 1 of the present application, and compounds XV-2 and XIV-2 prepared in Example 3;

[0038] Figure 14 This is the EPR spectrum of compound XIV-2 prepared in Example 3 of the present application;

[0039] Figure 15 It is the emission spectra of compound 1 and compound 2 prepared in example 1 of the present application in tetrahydrofuran. DETAILED DESCRIPTION

[0040] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the following is a further detailed description of this application in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application, but the implementation methods of this application are not limited thereto.

[0041] Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art. The experimental reagents used in the following examples, unless otherwise specified, are conventional biochemical reagents; the amounts of the experimental reagents used, unless otherwise specified, are the amounts used in routine experimental procedures; and the experimental methods, unless otherwise specified, are conventional methods.

[0042] In recent years, with the deepening of research on polycyclic aromatic hydrocarbons (PAHs), helical chiral PAHs with narrowband emission properties have attracted widespread attention. Narrowband emission generally refers to a compound's luminescence spectrum with a narrow full width at half maximum (FWHM), which makes these compounds have potential applications in display technology, bioimaging, and optical communications.

[0043] However, how to rationally design PAHs to have a narrow full-width at half-maximum (FWHM) emission spectrum, thereby improving the color purity of the device and enabling its application in organic light-emitting diodes, remains a major challenge.

[0044] This application synthesizes helical chiral polycyclic aromatic hydrocarbon compounds by using electron-rich mesitylene-substituted fluorene or electron-deficient trichlorobenzene-substituted fluorene fragments with terphenyl in a Suzuki reaction, followed by a Sholl reaction. These helical chiral polycyclic aromatic hydrocarbon compounds possess unique electronic and optical properties, particularly narrowband emission. Their luminescence spectra have a narrow full width at half maximum (FWHM), reaching 11 to 17 nm, and are suitable for applications in chemical sensors, optoelectronic devices, and biomedicine.

[0045] In the first aspect, the embodiments of the present application provide a helical chiral polycyclic aromatic hydrocarbon compound, the general structural formula of which is shown in Formula I: ; wherein R is selected from the following structures: 、 .

[0046] The helical chiral polycyclic aromatic hydrocarbon compounds provided in the embodiments of the present application, in terms of electronic structure, by alternating the arrangement of electron donor-acceptor substituents in the aromatic skeleton, allow frontier molecular orbitals (FMOs) to be localized above the atoms, which reduces the displacement of nuclear coordinates during electron transitions, suppresses the excitation of vibrational modes, and ultimately weakens the electron-vibration coupling effect; in terms of geometric configuration, they have a rigid luminescent plane that can limit the vibration amplitude of the molecule, which helps to further suppress vibrational coupling, thereby having a narrower emission spectrum. The full width at half maximum (FWHM) of its luminescence spectrum is relatively narrow, reaching 11nm~17nm, and can be applied to chemical sensors, optoelectronic devices, biomedicine and other fields.

[0047] In some embodiments, the above-mentioned helical chiral polycyclic aromatic hydrocarbon compound can be selected from the following compounds:

[0048] 、 .

[0049] Wherein, "tBu" in the above structural formula represents tert-butyl group.

[0050] The full width at half maximum (FWHM) of the emission spectrum of the compound 1 can reach 17 nm, and the full width at half maximum (FWHM) of the emission spectrum of the compound 2 can be 11 nm.

[0051] In a second aspect, the present invention further provides a method for preparing the helical chiral polycyclic aromatic hydrocarbon compound of the first aspect, comprising the following steps:

[0052] ;

[0053] Wherein, R is selected from the following structures: 、 ;

[0054] Synthesis of compound IV:

[0055] Compound II reacts with compound III in a first solvent in the presence of a first base and a first catalyst to obtain compound IV;

[0056] Synthesis of compound Ⅰ:

[0057] The compound IV is dissolved in a second solvent to obtain a first solution, and then a ferric chloride solution is added dropwise to the first solution, and the mixture is stirred and reacted at a first temperature to obtain compound I.

[0058] In some embodiments, in the synthesis step of Compound IV, the first base is potassium carbonate. The first catalyst is tetrakis(triphenylphosphine)palladium. The first solvent is a mixture of 1,4-dioxane and water. For example, the first solvent can be a mixture of 1,4-dioxane and water in a volume ratio of 4:1.

[0059] In some embodiments, when R represents When, the structural formula of compound III is shown in formula III-1: The structural formula of compound IV is shown in Formula IV-1: .

[0060] The preparation steps of the compound IV-1 are as follows: compound II, compound III-1, tetrakis(triphenylphosphine)palladium, and potassium carbonate are placed in a reaction bottle, a first solvent (a mixed solvent of 1,4-dioxane and water with a volume ratio of 4:1) is added, and frozen deoxygenation is carried out under nitrogen protection. After deoxygenation, the mixture is heated to 110°C and stirred for reaction for at least 36 hours. After the reaction, the mixture is extracted three times with dichloromethane, the organic phases are combined, and purification is carried out by column chromatography (petroleum ether: dichloromethane = 5:1) to obtain compound IV-1.

[0061] In other embodiments, when R represents When, the structural formula of compound III is shown in formula III-2: The structural formula of compound IV is shown in Formula IV-2: .

[0062] The preparation steps of compound IV-2 are as follows: compound II, compound III-2, tetrakis(triphenylphosphine)palladium, potassium carbonate, and tetrabutylammonium bromide are placed in a reaction bottle, a first solvent (a mixed solvent of 1,4-dioxane and water with a volume ratio of 4:1) is added, and the mixture is frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture is heated to 110°C and stirred for reaction for at least 36 hours. After the reaction, the mixture is extracted three times with dichloromethane, the organic phases are combined, and the mixture is purified by column chromatography (petroleum ether: dichloromethane = 5:1) to obtain compound IV-2.

[0063] In the step of preparing compound IV-2, it is necessary to ensure that 1,4-dioxane is anhydrous and the reaction time is not less than 36 hours. If the reaction time is less than 36 hours, the yield will be greatly reduced.

[0064] In some embodiments, in the synthesis step of Compound I, the second solvent is anhydrous dichloromethane; and the first temperature is room temperature (usually 25° C.).

[0065] As an example, the preparation steps of compound I are as follows: under a nitrogen atmosphere, compound IV is dissolved in anhydrous dichloromethane to obtain a first solution; ferric chloride is dissolved in nitromethane under a nitrogen atmosphere to obtain a ferric chloride solution, and the ferric chloride solution is then added dropwise to the above-mentioned first solution, followed by stirring and reacting at a first temperature (25°C) for 30 minutes to 1 hour; after the reaction is completed, methanol is added to quench the reaction, and the solvent is removed and purified by column chromatography (petroleum ether: dichloromethane = 2:1) to obtain compound I.

[0066] In the step of preparing compound I, the molar ratio of compound IV to ferric chloride is 10-295.

[0067] In some embodiments, the preparation steps of Compound II include:

[0068] ;

[0069] Synthesis of compound VI:

[0070] Dissolving compound V in a third solvent at a second temperature, adding a sodium nitrite aqueous solution, then adding a potassium iodide solution dropwise and heating to a third temperature, and continuously stirring the reaction until the reaction is complete to obtain compound VI;

[0071] Synthesis of compound II:

[0072] At a fourth temperature, compound VI reacts with 1,4-phenylenediboronic acid in a fourth solvent in the presence of a second base and a second catalyst to obtain compound II.

[0073] In some embodiments, in the synthesis step of compound VI, the third solvent is hydrochloric acid with a concentration of 6 mol / L; the second temperature is 0° C.; and the third temperature is room temperature (usually 25° C.).

[0074] As an example, the preparation steps of compound VI are as follows:

[0075] Compound V was dissolved in hydrochloric acid (concentration of 6 mol / L) and kept at a constant temperature of 0°C for 30 minutes to obtain a second solution; sodium nitrite was dissolved in distilled water to prepare a sodium nitrite aqueous solution, and the sodium nitrite aqueous solution was added to the second solution, and stirred at 0°C for 30 minutes to obtain a third solution; potassium iodide was dissolved in ice water to prepare a potassium iodide solution; the potassium iodide solution was added dropwise to the third solution, and the temperature was slowly raised to room temperature (usually 25°C), and the reaction was continued with stirring (mechanical stirring) for 6 hours. After the reaction was completed, ice water and a 30% by mass sodium bisulfite solution were added to the reaction system to quench the reaction, and then extracted three times with dichloromethane. The organic phases were combined and the product was purified by column chromatography (petroleum ether) to obtain compound VI.

[0076] In the step of synthesizing compound VI, since the reaction system becomes viscous after the addition of potassium iodide solution, mechanical stirring or appropriately extending the reaction time can ensure the complete reaction.

[0077] In some embodiments, in the synthesis step of compound II, the second base is at least one of sodium bicarbonate and potassium bicarbonate; the second catalyst is 1,1'-bisdiphenylphosphinoferrocenepalladium dichloride; the fourth solvent is a mixed solvent of dimethyl sulfoxide and water; and the fourth temperature is 85°C.

[0078] As an example, the preparation steps of compound II are as follows:

[0079] Compound VI, 1,4-phenylenediboronic acid, 1,1'-bis(diphenylphosphinoferrocenepalladium dichloride) and sodium bicarbonate were placed in a reaction flask, and a fourth solvent (a mixed solvent of dimethyl sulfoxide and water in a volume ratio of 6:1) was added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 85°C and stirred for at least 72 hours. After the reaction, the mixture was extracted three times with ethyl acetate, the organic phases were combined, and purified by column chromatography (petroleum ether) to obtain compound II.

[0080] In the synthesis step of compound II, the stirring reaction time is at least 72 hours. When the stirring reaction time is less than 72 hours, the yield will be greatly reduced.

[0081] In some embodiments, when R represents When the compound III has the structural formula shown in formula III-1: The synthesis steps of compound III-1 include:

[0082] ;

[0083] Synthesis of compound IX:

[0084] At a fifth temperature, compound VII reacts with compound VIII in a fifth solvent in the presence of a third catalyst and a third base to obtain compound IX;

[0085] Synthesis of Compound X:

[0086] Dissolving the compound IX in a sixth solvent, and adding 2,4,6-trimethylphenylmagnesium bromide dropwise under a nitrogen atmosphere, stirring the reaction until the reaction is complete, quenching the reaction, and removing the solvent to obtain a first crude product, dissolving the first crude product in a seventh solvent, and then adding boron trifluoride diethyl ether complex dropwise to react to obtain compound X;

[0087] Synthesis of compound III-1:

[0088] The compound X reacts with biboric acid pinacol ester in an eighth solvent in the presence of a fourth base and a fourth catalyst to obtain compound III-1.

[0089] In some embodiments, in the synthesis step of compound IX, the third catalyst is tetrakis(triphenylphosphine)palladium; the third base is at least one of sodium carbonate and potassium carbonate; the fifth solvent is a mixed solvent of toluene, ethanol and water; and the fifth temperature is 80°C.

[0090] As an example, the preparation steps of compound IX are as follows:

[0091] Compound VII, compound VIII, tetrakis(triphenylphosphine)palladium, and sodium carbonate were placed in a reaction flask, and a fifth solvent (a mixed solvent of toluene, ethanol, and water in a volume ratio of 4:2:1) was added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 80°C and stirred overnight. After the reaction, the mixture was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether:ethyl acetate = 10:1) to obtain compound IX.

[0092] In some embodiments, in the step of synthesizing compound X, the sixth solvent is anhydrous tetrahydrofuran; and the seventh solvent is dichloromethane.

[0093] As an example, the preparation steps of compound X are as follows:

[0094] Compound IX was dissolved in anhydrous tetrahydrofuran, and 2,4,6-trimethylphenylmagnesium bromide was added dropwise at room temperature under a nitrogen atmosphere. The reaction was stirred at room temperature (usually 25°C) for 24 hours. After the reaction was completed, a saturated ammonium chloride solution was added to quench the reaction, and then extracted three times with dichloromethane. The solvent was removed to obtain a first crude product; the first crude product was dissolved in dichloromethane, and boron trifluoride ether complex was added dropwise under a nitrogen atmosphere. Stirring was continued at room temperature for 10 minutes. After the reaction was completed, a saturated ammonium chloride solution was added to quench the reaction, and then extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether) to obtain compound X.

[0095] In the step of synthesizing compound X, the reaction system must be kept free of water and oxygen, and the boron trifluoride etherate compound should be added dropwise.

[0096] In some embodiments, in the synthesis step of compound III-1, the fourth base is potassium acetate; the fourth catalyst is 1,1'-bisdiphenylphosphinoferrocenepalladium dichloride; and the eighth solvent is 1,4-dioxane.

[0097] As an example, the synthesis steps of compound III-1 are as follows:

[0098] Compound X, pinacol borate, potassium acetate and 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride were placed in a reaction flask, and the eighth solvent (1,4-dioxane) was added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 100°C and stirred for at least 36 hours. After the reaction, the mixture was extracted three times with dichloromethane, the organic phases were combined, and purified by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain compound III-1.

[0099] In the step of preparing compound III-1, the eighth solvent is anhydrous 1,4-dioxane, and the stirring reaction time is not less than 36 hours. If the stirring reaction time is less than 36 hours, the yield will be greatly reduced.

[0100] In some embodiments, when R represents When, the structural formula of the compound III is shown in formula III-2: .

[0101] Among them, the synthetic route of compound III-2 is as follows:

[0102] ;

[0103] Synthesis of compound XIII:

[0104] Compound XII is dissolved in a ninth solvent, maintained at a sixth temperature, and then an n-butyllithium solution is added dropwise thereto, stirred for reaction, and then compound XI is added and the temperature is raised to a seventh temperature. The reaction is continued with stirring until the reaction is complete, the reaction is quenched, and the solvent is removed to obtain a second crude product. The second crude product is dissolved in a seventh solvent, and then boron trifluoride etherate complex and triethylsilane are added dropwise thereto for reaction to obtain compound XIII.

[0105] Synthesis of compound III-2:

[0106] The compound XIII is reacted with pinacol diborate in an eighth solvent in the presence of a fourth base and a fourth catalyst to obtain compound III-2.

[0107] In some embodiments, in the synthesis step of compound XIII, the ninth solvent is anhydrous tetrahydrofuran; the sixth temperature is -78°C; and the seventh temperature is -55°C.

[0108] As an example, the preparation steps of compound XIII are as follows:

[0109] Under a nitrogen atmosphere, compound XII was dissolved in anhydrous tetrahydrofuran and kept constant temperature in a cryostat at -78°C for 30 minutes. Then, n-butyllithium solution was added dropwise thereto, and the reaction was continued with stirring at this temperature for 30 minutes. Compound XI was then added and the temperature was raised to -55°C. The reaction was continued with stirring for 16 hours. After the reaction, a saturated ammonium chloride solution was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The solvent was removed to obtain a second crude product. The second crude product was dissolved in dichloromethane, and boron trifluoride ether complex and triethylsilane were added dropwise thereto. The reaction was stirred at room temperature for 4 hours. After the reaction, a saturated ammonium chloride solution was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether) to obtain compound XIII.

[0110] During the synthesis of Compound XIII, the reaction system must be anhydrous and oxygen-free, and the boron trifluoride etherate should be added dropwise. Subsequent reactions can proceed smoothly under both air and nitrogen conditions after the addition of the boron trifluoride etherate and triethylsilane.

[0111] In some embodiments, in the synthesis step of Compound III, the fourth base is potassium acetate; the fourth catalyst is 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride; the eighth solvent is 1,4-dioxane; the reaction temperature is 100°C, and the stirring reaction time is at least 36 hours. If the stirring reaction time is less than 36 hours, the yield will be significantly reduced.

[0112] As an example, the preparation steps of compound III-2 are as follows:

[0113] Compound XIII, pinacol borate, potassium acetate, and 1,1'-bis(diphenylphosphinoferrocene)palladium dichloride were placed in a reaction flask, and anhydrous 1,4-dioxane was added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 100°C and stirred for at least 36 hours. After the reaction, the mixture was extracted three times with dichloromethane, and the organic phases were combined and purified by column chromatography (petroleum ether: ethyl acetate = 20:1) to obtain compound III-2.

[0114] Open-shell compounds often exhibit high reactivity due to the presence of unpaired electrons. For example, in organic synthesis, open-shell free radicals can participate in a variety of reactions, such as addition and substitution reactions, thereby synthesizing organic compounds with specific structures. Furthermore, the unpaired electrons in open-shell compounds can lead to magnetic properties. For example, certain compounds can exhibit open-shell structural properties upon oxidation, suggesting their potential application in magnetic materials.

[0115] Open-shell compounds are compounds with unpaired electrons, and their electronic ground state is an open-shell structure. Compared with closed-shell compounds, open-shell compounds have unique physicochemical properties. Although studies have been conducted to introduce helical chiral structures and free radical properties into polycyclic aromatic hydrocarbons, current synthesis methods often have many limitations. For example, some polycyclic aromatic hydrocarbon compounds with introduced free radical properties are prone to degradation during the redox process, which limits their stability in practical applications. In addition, most existing compounds have relatively single functions and are difficult to meet multiple application requirements at the same time. Therefore, the development of a new type of open-shell helical chiral polycyclic aromatic hydrocarbon compound through rational design of structure and synthesis method to achieve the regulation of its free radical properties has important scientific significance and practical application value.

[0116] In a third aspect, an embodiment of the present application further provides an open-shell compound, which is prepared from the helical chiral polycyclic aromatic hydrocarbon compound of the first aspect by chemical oxidation.

[0117] The technical solution provided in the embodiments of this application can regulate the free radical properties of helical chiral polycyclic aromatic hydrocarbons by oxidizing the hydrogen atoms on the fluorene groups of the compounds, thereby stably generating their ionic and free radical structures. This oxidation reaction not only changes the electronic structure of the molecule but also introduces new chemically active sites, thereby endowing the compound with new functions.

[0118] The open-shell compounds provided in the embodiments of the present application have unique electronic and optical properties and can be applied in fields such as chemical sensors, optoelectronic devices, and biomedicine.

[0119] In some embodiments, the open-shell compound has the general structural formula shown in Formula XIV: ; wherein R is selected from the following structures: 、 .

[0120] When R is selected from When, the structural formula of the open-shell compound is shown in Formula XIV-1: .

[0121] When R is selected from When , the structural formula of the open-shell compound is shown in Formula XIV-2: .

[0122] In a fourth aspect, the present invention further provides a method for preparing the open-shell compound of the third aspect, comprising the following steps:

[0123] ;

[0124] Synthesis of compound XV:

[0125] Under nitrogen atmosphere, compound I is dissolved in the tenth solvent, and n-butyl lithium is added dropwise to generate compound XV in situ;

[0126] Synthesis of compound XIV:

[0127] Iodine is added to the compound XV to generate compound XIV in situ.

[0128] In some embodiments, in the step of synthesizing compound XV, the tenth solvent is anhydrous tetrahydrofuran.

[0129] As an example, the preparation steps of compound XV are as follows:

[0130] Under nitrogen atmosphere, compound I is dissolved in anhydrous tetrahydrofuran, and n-butyl lithium is added dropwise at room temperature (usually 25°C) to generate compound XV in situ.

[0131] The preparation steps of compound XIV are as follows:

[0132] Iodine is added to the compound XV prepared above to generate compound XIV in situ.

[0133] In the steps of preparing compound XV and compound XIV, the reaction system needs to be strictly controlled to be an anhydrous and oxygen-free system, otherwise the preparation will fail and no product will be obtained.

[0134] In a fifth aspect, the embodiments of the present application further provide the use of the helical chiral polycyclic aromatic hydrocarbon compound of the first aspect or the open-shell compound of the third aspect in the preparation of chemical sensors and optoelectronic devices.

[0135] The present application has been subjected to multiple tests, and part of the test results are cited as a reference to further describe the invention in detail, which will be described in detail in conjunction with specific embodiments.

[0136] Example 1

[0137] ;

[0138] Step 1: Synthesis of Compound VI

[0139] Compound V (6.14 g, 20 mmol) was added to a 250 mL round-bottom flask, along with 20 mL of HCl (6 mol / L), stirred to dissolve, and maintained at 0°C for 30 minutes. Sodium nitrite (2.76 g, 40 mmol) was dissolved in 20 mL of distilled water to prepare a sodium nitrite aqueous solution, which was added to the round-bottom flask and stirred at 0°C for 30 minutes. Potassium iodide (6.64 g, 40 mmol) was then dissolved in 20 mL of ice water to prepare a potassium iodide solution, which was then added dropwise to the round-bottom flask and slowly warmed to room temperature. Vigorous stirring was continued for 6 hours. After the reaction, ice water and 30% sodium bisulfite solution were added to the reaction system to quench the reaction. The product was extracted three times with dichloromethane, and the organic phases were combined and purified by column chromatography (petroleum ether) to obtain 5.0 g of a yellow oily liquid, namely, compound VI, with a yield of 60%.

[0140] The obtained yellow oily liquid (Compound VI) was identified, and its H NMR spectrum data was as follows: 1 H NMR (400 MHz, CDCl3) δ: 7.55 (s, 2H), 1.27 (s, 9H).

[0141] Step 2: Synthesis of Compound II

[0142] Compound VI (4.18 g, 10 mmol), 1,4-phenylenediboronic acid (0.83 g, 5 mmol), 1,1'-bis(diphenylphosphinoferrocenepalladium) dichloride (0.122 g, 0.15 mmol), and sodium bicarbonate (2.52 g, 30 mmol) were placed in a reaction flask, and 120 mL of dimethyl sulfoxide and 20 mL of distilled water were added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 85°C and stirred for 72 hours. After the reaction, the mixture was extracted three times with ethyl acetate. The organic phases were combined and purified by column chromatography (petroleum ether) to obtain 1.48 g of a white solid, namely, compound II, with a yield of 45%.

[0143] The obtained white solid (i.e., compound II) was identified, and its H NMR spectrum data was as follows: 1 H NMR (500 MHz, CDCl3) δ :7.64 (s, 4H), 7.27 (s, 4H), 1.36 (s, 18H).

[0144] ;

[0145] Step 3: Synthesis of Compound IX

[0146] Compound VII (2.36 g, 10 mmol), compound VIII (1.65 g, 11 mmol), tetrakis(triphenylphosphine)palladium (57.8 mg, 0.05 mmol), and sodium carbonate (2.12 g, 20 mmol) were placed in a reaction flask, and 40 mL of toluene, 20 mL of ethanol, and 10 mL of distilled water were added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 80°C and stirred overnight. After the reaction was completed, the mixture was extracted three times with dichloromethane, and the organic phases were combined and purified by column chromatography (petroleum ether:ethyl acetate = 10:1) to obtain 1.69 g of a white solid, namely, compound IX, with a yield of 65%.

[0147] The obtained white solid (i.e., compound IX) was identified, and its H NMR spectrum data was as follows: 1 H NMR (400 MHz, CDCl3) δ :9.97 (s, 1H), 8.02 (dd, J = 7.8, 1.0 Hz, 1H), 7.64 (ddd, J =12.1, 9.1, 4.9 Hz, 3H), 7.51 (dd, J = 4.5, 2.9 Hz, 1H), 7.41 (dd, J = 7.7, 0.6Hz, 1H), 7.26 (dd,J = 6.1, 2.3 Hz, 2H).

[0148] Step 4: Synthesis of Compound X

[0149] Compound IX (4 g, 15.32 mmol) was dissolved in 35 mL of anhydrous tetrahydrofuran. Under a nitrogen atmosphere, 2,4,6-trimethylphenylmagnesium bromide (30.64 mL, 1 M in THF) was added dropwise at room temperature and stirred for 24 hours. After completion of the reaction, saturated ammonium chloride solution was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The solvent was removed to obtain a first crude product. This first crude product was dissolved in 50 mL of dichloromethane, and boron trifluoride etherate was added dropwise under a nitrogen atmosphere. The reaction was stirred at room temperature for another 10 minutes. After completion of the reaction, saturated ammonium chloride solution was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether) to obtain 4.49 g of a white solid, Compound X, in an 81% yield.

[0150] The obtained compound X was identified, and its H NMR spectrum data were as follows: 1 H NMR (500 MHz,CDCl3) δ :7.77 (d, J = 7.6 Hz, 1H), 7.65 (d, J = 8.1 Hz, 1H), 7.51 – 7.47 (m, 1H), 7.41 – 7.31 (m, 2H), 7.24 (dd, J = 7.3, 0.9 Hz, 1H), 7.19 (d, J = 7.5 Hz, 1H), 7.01 (s, 1H), 6.65 (s, 1H), 5.44 (s, 1H), 2.64 (s, 3H), 2.27 (s, 3H), 1.09 (s, 3H).

[0151] Step 5: Synthesis of Compound III-1

[0152] Compound X (1.09 g, 3 mmol), pinacol diboronate (0.838 g, 3.3 mmol), potassium acetate (0.88 g, 9 mmol), and 1,1'-bis(diphenylphosphinoferrocenedichloropalladium) (109.71 mg, 5 mol) were placed in a reaction flask. 20 mL of 1,4-dioxane was added, and the mixture was frozen and deoxygenated under nitrogen. After deoxygenation, the mixture was heated to 100°C and stirred for 36 hours. After the reaction, the mixture was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether:ethyl acetate = 20:1) to obtain 923 mg of a white solid, namely, compound III-1, with a yield of 75%.

[0153] The obtained compound III-1 was identified, and its H NMR spectrum data were as follows: 1 H NMR (500 MHz,CDCl3) δ :7.85 (q, J = 7.8 Hz, 33H), 7.67 (d, J = 0.6 Hz, 1H), 7.38 (t, J = 7.4 Hz,1H), 7.27 – 7.23 (m, 1H), 7.19 (dd, J = 7.5, 0.5 Hz, 1H), 7.01 (s, 1H), 6.63(s, 1H), 5.48 (s, 1H), 2.68 (s, 3H), 2.28 (s, 3H), 1.33 (s, 12H), 1.07 (s,3H).

[0154] The synthetic route of compound 1 is as follows:

[0155] ;

[0156] Step 6: Synthesis of Compound IV-1

[0157] Compound II (657.87 mg, 1 mmol), compound III-1 (2.05 g, 5 mmol), tetrakis(triphenylphosphine)palladium (116 mg, 0.1 mmol), and potassium carbonate (1.66 g, 12 mmol) were placed in a reaction flask, and 12 mL of 1,4-dioxane and 4 mL of distilled water were added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, it was heated to 110 °C and stirred for 36 hours. After the reaction, it was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether: dichloromethane = 5:1) to obtain 1.1 g of white solid, namely compound IV-1, with a yield of 75%.

[0158] The compound IV-1 obtained above was identified, and its H NMR spectrum data was as follows: 1 H NMR (500MHz, CDCl3) δ :7.81 – 7.61 (m, 4H), 7.45 – 7.33 (m, 8H), 7.29 – 7.17 (m, 20H), 7.00 (d, J = 7.0 Hz, 4H), 6.75 – 6.60 (m, 8H), 5.49 (dd, J = 27.9, 17.0 Hz, 4H),2.64 (dt, J = 22.1, 14.7 Hz, 12H), 2.28 (dd, J = 12.5, 3.9 Hz, 12H), 1.41 – 1.31(m, 12H), 1.31 – 1.23 (m, 18H).

[0159] Step 7: Synthesis of compound 1

[0160] Under a nitrogen atmosphere, compound IV-1 (32.38 mg, 0.022 mmol) was dissolved in 30 mL of anhydrous dichloromethane to obtain a third solution. Ferric chloride (95 mg, 0.59 mmol) was dissolved in nitromethane (1 mL) under a nitrogen atmosphere to obtain a ferric chloride solution. The ferric chloride solution was added dropwise to the third solution, and the third solution was stirred at room temperature for 30 minutes. After the reaction was completed, methanol was added to quench the reaction. After removing the solvent, the product was purified by column chromatography (petroleum ether: dichloromethane = 2:1) to obtain 10.92 mg of a yellow solid, namely, compound 1, with a yield of 34%.

[0161] Compound 1 prepared above was identified using a 500 MHz Bruker Avance NMR spectrometer and a Chloroform-d solution. The H NMR spectrum of the compound was as follows: Figure 1 As shown, the H NMR spectrum data is:

[0162] 1 H NMR (500 MHz, CDCl3) δ 9.05 (s, 4H), 8.90 (s, 4H), 7.74 (d, J = 8.0 Hz,4H), 7.09 (s, 8H), 7.00 – 6.94 (m, 4H), 6.81 (t, J= 7.4 Hz, 4H), 6.45 (s, 4H), 6.18 (s, 4H), 3.00 (s, 12H), 2.21 (s, 12H), 1.66 (s, 12H), 1.47 (s, 18H).

[0163] The compound 1 prepared above was tested using a Bruker AutoFlex MAX matrix-assisted laser desorption time-of-flight mass spectrometer. The high-resolution mass spectrum was as follows: Figure 2 As shown, the molecular formula is C 114 H 90 , the theoretical value is 1459.7076, and the actual test value is 1459.7064.

[0164] ;

[0165] Step 8: Synthesis of Compound XIII

[0166] Under a nitrogen atmosphere, compound XII (3.15 g, 17.4 mmol) was dissolved in 30 mL of tetrahydrofuran and maintained in a cryostat at -78°C for 30 minutes. Then, n-butyllithium solution (2.4 M in Hexane, 5.79 mL) was added dropwise. The reaction was stirred at this temperature for 30 minutes. Compound XI (3 g, 11.6 mmol) was then added, and the temperature was raised to -55°C, where it was stirred for 16 hours. After completion of the reaction, saturated ammonium chloride solution was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The solvent was removed to obtain a second crude product. This second crude product was dissolved in dichloromethane, and boron trifluoride etherate (3 mL) and triethylsilane (3.6 mL, 23.3 mmol) were added dropwise. The reaction was stirred at room temperature for 4 hours. After the reaction was completed, saturated ammonium chloride solution was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether) to obtain 4.67 g of a pink solid, namely compound XIII, with a yield of 92%.

[0167] The pink solid (i.e., Compound XIII) obtained above was identified, and its H NMR spectrum data was as follows: 1 H NMR (400 MHz, CDCl3) δ :7.76 (d, J = 7.6 Hz, 1H), 7.64 (d, J = 8.1 Hz, 1H), 7.53– 7.49 (m, 2H), 7.39 (t, J= 7.5 Hz, 1H), 7.32 (s, 1H), 7.27 (dd, J = 10.9, 4.0Hz, 1H), 7.18 (d, J = 7.5 Hz, 1H), 7.12 (d, J = 2.1 Hz, 1H), 5.87 (s, 1H).

[0168] Step 9: Synthesis of Compound III-2

[0169] Compound XIII (2 g, 4.71 mmol), pinacol diboron (1.43 g, 5.65 mmol), potassium acetate (2.8 g, 28.3 mmol), and 1,1'-bis(diphenylphosphinoferrocenedichlorid)palladium (100 mg, 0.138 mmol) were placed in a reaction flask, and 30 mL of 1,4-dioxane was added. The mixture was deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 100°C and stirred for 36 hours. After the reaction, the mixture was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether:ethyl acetate = 20:1) to obtain 1.53 g of a white solid, compound III-2, in a yield of 67%.

[0170] The compound III-2 prepared above was identified, and its H NMR spectrum data was as follows:

[0171] 1 H NMR (500 MHz, CDCl3) δ :7.89 (dd, J = 7.6, 0.8 Hz, 1H), 7.83 (dd, J =8.8, 8.2 Hz, 2H), 7.63 (d, J = 0.7 Hz, 1H), 7.52 (d, J = 2.2 Hz, 1H), 7.41 (t, J =7.5 Hz, 1H), 7.31 – 7.26 (m, 1H), 7.20 (d, J = 7.5 Hz, 1H), 7.11 (d, J = 2.1 Hz,1H), 5.91 (s, 1H), 1.34 (s, 12H).

[0172] The synthetic route of compound 2 is as follows:

[0173] ;

[0174] Step 10: Synthesis of Compound IV-2

[0175] Compound II (657.87 mg, 1 mmol), compound III-2 (2.43 g, 5 mmol), tetrakis(triphenylphosphine)palladium (36 mg, 0.031 mmol), potassium carbonate (1.1 g, 8 mmol), and tetrabutylammonium bromide (68 mg, 0.21 mmol) were placed in a reaction flask, and 20 mL of toluene and 5 mL of distilled water were added. The mixture was frozen and deoxygenated under nitrogen protection. After deoxygenation, the mixture was heated to 110°C and stirred for 36 hours. After the reaction, it was extracted three times with dichloromethane. The organic phases were combined and purified by column chromatography (petroleum ether: dichloromethane = 3:1) to obtain 1.1 g of a white solid, namely compound IV-2, with a yield of 84%.

[0176] The compound IV-2 prepared above was identified, and its H NMR spectrum data was as follows:

[0177] 1 H NMR (400 MHz, CDCl3) δ :7.39 – 7.26 (m, 16H), 7.13 – 7.08 (m, 8H), 7.05 – 6.97 (m, 8H), 6.92 – 6.85 (m, 4H), 6.68 – 6.60 (m, 8H), 6.32 (s, 4H), 6.04 (s, 4H), 1.23 (s, 18H).

[0178] Step 11: Synthesis of Compound 2

[0179] Under a nitrogen atmosphere, compound IV-2 (37.78 mg, 0.022 mmol) was dissolved in 30 mL of anhydrous dichloromethane to obtain a fourth solution. Ferric chloride (95 mg, 0.59 mmol) was dissolved in nitromethane (1 mL) under a nitrogen atmosphere to obtain a ferric chloride solution. The ferric chloride solution was added dropwise to the fourth solution, and the fourth solution was then stirred at room temperature for 30 minutes. After the reaction was completed, methanol was added to quench the reaction. After removing the solvent, the product was purified by column chromatography (petroleum ether: dichloromethane = 2:1) to obtain 10.13 mg of a yellow solid, namely, compound 2, with a yield of 27%.

[0180] Compound 2 prepared above was identified using a 500 MHz Bruker Avance NMR spectrometer and a Chloroform-d solution. The H NMR spectrum of the compound was as follows: Figure 3 As shown, its nuclear magnetic resonance hydrogen spectrum data is:

[0181] 1 H NMR (500 MHz, CDCl3) δ :9.16 (s, 4H), 8.95 (s, 4H), 7.80 (d, J = 8.0Hz, 4H), 7.70 (s, 4H), 7.14 (d, J = 7.3 Hz, 4H), 7.08 (t, J = 7.2 Hz, 4H), 7.02(s, 4H), 6.93 (t, J = 7.3 Hz, 4H), 6.68 (s, 4H), 1.77 (s, 18H).

[0182] The compound 2 prepared above was tested using a Bruker AutoFlex MAX matrix-assisted laser desorption time-of-flight mass spectrometer. The high-resolution mass spectrum was as follows: Figure 4 As shown. Figure 4 It can be seen that the molecular formula of compound 2 is C 102 H 54 Cl 12 , the theoretical value is 1705.0433, and the actual test value is 1705.0437.

[0183] Example 2

[0184] ;

[0185] Step 1: Synthesis of Compound XV-1

[0186] Under a nitrogen atmosphere, compound 1 (6.6 mg, 0.0045 mmol) was placed in a round-bottom flask, 3 mL of anhydrous tetrahydrofuran was added, and n-butyl lithium (1.6 M in Hexane, 12 μL) was added dropwise at room temperature to obtain a green solution in situ to obtain compound XV-1.

[0187] Step 2: Synthesis of Compound XIV-1

[0188] Iodine (5 mg, 0.018 mmol) was added to compound XV-1 obtained in the first step above, and the solution color turned brown, indicating that compound XIV-1 was generated in situ.

[0189] Example 3

[0190] ;

[0191] Step 1: Synthesis of Compound XV-2

[0192] Under a nitrogen atmosphere, compound 2 (7.7 mg, 0.0045 mmol) was placed in a round-bottom flask, 3 mL of anhydrous tetrahydrofuran was added, and n-butyllithium (1.6 M in hexane, 12 μL) was added dropwise at room temperature to obtain a green solution in situ, which was compound XV-2.

[0193] Step 2: Synthesis of Compound XIV-2

[0194] Iodine (5 mg, 0.018 mmol) was added to the compound XV-2 obtained above, and the color of the solution turned brown, indicating that compound XIV-2 was generated in situ.

[0195] Example 4

[0196] Compound 1 prepared in Example 1 was dissolved in five solvents with different polarities, namely, n-hexane, toluene, tetrahydrofuran (THF), dichloromethane (DCM), and ether, at a concentration of 1×10 - 5 mol / L solution, and the absorption spectrum was tested using Jasco-V 770 spectrophotometer. The test results are as follows Figure 5 shown.

[0197] from Figure 5 It can be seen that compound 1 has similar absorption peaks and exhibits similar absorption characteristics in solvents of different polarities, with the maximum absorption peak located at around 508 nm.

[0198] Example 5

[0199] Compound 1 prepared in Example 1 was dissolved in five solvents with different polarities, namely, n-hexane, toluene, tetrahydrofuran (THF), dichloromethane (DCM), and ether, at a concentration of 1×10 -5 mol / L solution, the emission spectrum of various solutions was tested using a Lingguang Tech F97 Pro fluorescence spectrometer. The test results are as follows Figure 6 shown.

[0200] from Figure 6 It can be seen that compound 1 has a narrow half-peak width, which can reach 17 nm in THF.

[0201] Example 6

[0202] Compound 1 obtained in Example 1 was separated by column chromatography to obtain its enantiomers. The obtained enantiomers were tested by circular dichroism. The test results were as follows: Figure 7 shown.

[0203] from Figure 7 It can be seen that the circular dichroism spectrum of compound 1 at room temperature has an obvious Cotton effect. This method provides great convenience for the purification of enantiomers and also makes it possible to further study its chiral optical properties.

[0204] Example 7

[0205] Compound 2 prepared in Example 1 was dissolved in five solvents with different polarities, namely, n-hexane, toluene, tetrahydrofuran (THF), dichloromethane (DCM), and ether, at a concentration of 1×10 -5 mol / L solution, and the absorption spectrum was tested using Jasco-V 770 spectrophotometer. The test results are as follows Figure 8 shown.

[0206] from Figure 8 It can be seen that compound 2 has similar absorption peaks and exhibits similar absorption characteristics in solvents of different polarities, with the maximum absorption peak located at around 507 nm.

[0207] Example 8

[0208] Compound 2 prepared in Example 1 was dissolved in five solvents with different polarities, namely, n-hexane, toluene, tetrahydrofuran (THF), dichloromethane (DCM), and ether, at a concentration of 1×10 -5 mol / L solution, the emission spectrum of various solutions was tested using a Lingguang Tech F97 Pro fluorescence spectrometer. The test results are as follows Figure 9 shown.

[0209] from Figure 9 It can be seen that compound 2 has a narrow half-peak width, which can reach 11 nm in THF.

[0210] Example 9

[0211] Compound 2 prepared in Example 1 was separated by column chromatography to obtain its enantiomers. The obtained enantiomers were tested by circular dichroism. The test results were as follows: Figure 10 shown.

[0212] from Figure 10 It can be seen that the circular dichroism spectrum of compound 2 at room temperature has an obvious Cotton effect. This method provides great convenience for the purification of enantiomers and also makes it possible to further study its chiral optical properties.

[0213] Example 10

[0214] The compound XV-1 and compound XIV-1 prepared in Example 2 were diluted to a concentration of 1×10 -5 mol / L solution, and the absorption spectrum was tested using Jasco-V 770 spectrophotometer. The test results are as follows Figure 11 Compound XV-1 (anionic compound) showed new absorption peaks at 743 nm, 625 nm, and 576 nm, and the solution appeared green (as shown in Figure 2). Figure 11 Compound XIV-1 (open-shell compound) exhibited a characteristic absorption peak at 789 nm in the near-infrared region I, and the solution turned brown-red at this time.

[0215] Example 11

[0216] The compound XIV-1 prepared above was drawn into the glove box using a capillary tube with an inner diameter of 1 mm. After the tube was sealed with the capillary tube, the paramagnetic signal was characterized using a Bruker AV III HD-500 ESR instrument. The test results are shown in FIG. Figure 12 As shown in the figure, a paramagnetic signal appears at 3507 mT with a g value of 2.003. This is consistent with the UV-visible-near-infrared absorption spectrum, and the appearance of a new absorption peak indicates the formation of compound XIV-1.

[0217] Example 12

[0218] Compound XV-2 and Compound XIV-2 prepared in Example 3 were diluted to a concentration of 1×10 -5 mol / L solution, and the absorption spectrum was tested using Jasco-V 770 spectrophotometer. The test results are as follows Figure 13 As shown. Compound XV-2 (anionic compound) showed a new absorption peak at 613 nm, and the solution was earthy yellow (as shown Figure 13 Compound XIV-2 (open-shell compound) exhibits a characteristic absorption peak at 815 nm in the near-infrared region I, at which point the solution turns brownish red (as shown). Figure 13 shown).

[0219] Example 13

[0220] The compound XIV-2 prepared above was drawn into the glove box using a capillary tube with an inner diameter of 1 mm. After the tube was sealed with the capillary tube, the paramagnetic signal was characterized using a Bruker AV III HD-500 ESR instrument. The test results are shown in FIG. Figure 14 As shown in the figure, a paramagnetic signal appears at 3507 mT with a g value of 2.003. This is consistent with the UV-visible-near-infrared absorption spectrum, and the appearance of a new absorption peak indicates the formation of compound XIV-2.

[0221] Example 14

[0222] Compounds 1 and 2 prepared in Example 1 were dissolved in tetrahydrofuran (THF) to a concentration of 1×10 -5 mol / L solution, the emission spectrum of the solution was tested using a Lingguang Tech F97 Pro fluorescence spectrometer. The test results are as follows Figure 15 shown.

[0223] from Figure 15 The emission peaks of compounds 1 and 2 are both located at 507-508 nm, with compound 2 exhibiting a full width at half maximum of 11 nm. This indicates that by varying the substituents in helical chiral polycyclic aromatic hydrocarbons, the charge distribution and energy level structure of the molecules can be adjusted, thereby regulating their luminescence characteristics and, further, their electronic structure and optical properties. These compounds can be used in the preparation of optical devices such as OLEDs and chemical sensors.

[0224] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present application, and should all be included in the scope of protection of the present application.

Claims

1. A helical chiral polycyclic aromatic hydrocarbon compound, characterized in that: Its general structural formula is shown in Formula I: ； Wherein, R is selected from the following structures: 、 .

2. A method for preparing a helical chiral polycyclic aromatic hydrocarbon compound according to claim 1, characterized in that: The steps include: ； Wherein, R is selected from the following structures: 、 ; Synthesis of compound IV: Compound II reacts with compound III in a first solvent in the presence of a first base and a first catalyst to obtain compound IV; Synthesis of compound Ⅰ: The compound IV is dissolved in a second solvent to obtain a first solution, and then a ferric chloride solution is added dropwise to the first solution, and the mixture is stirred and reacted at a first temperature to obtain compound I.

3. The method for preparing a helical chiral polycyclic aromatic hydrocarbon compound according to claim 2, wherein: The preparation steps of compound II include: ； Synthesis of compound VI: Dissolving compound V in a third solvent at a second temperature, adding a sodium nitrite aqueous solution, then adding a potassium iodide solution dropwise and heating to a third temperature, and continuously stirring the reaction until the reaction is complete to obtain compound VI; Synthesis of compound II: At a fourth temperature, compound VI reacts with 1,4-phenylenediboronic acid in a fourth solvent in the presence of a second base and a second catalyst to obtain compound II.

4. The method for preparing a helical chiral polycyclic aromatic hydrocarbon compound according to claim 2, wherein: When R stands for When the compound III has the structural formula shown in formula III-1: ; The synthesis steps of the compound III-1 include: ； Synthesis of compound IX: At a fifth temperature, compound VII reacts with compound VIII in a fifth solvent in the presence of a third catalyst and a third base to obtain compound IX; Synthesis of Compound X: Dissolving the compound IX in a sixth solvent, and adding 2,4,6-trimethylphenylmagnesium bromide dropwise under a nitrogen atmosphere with stirring, quenching the reaction after completion, and removing the solvent to obtain a first crude product, dissolving the first crude product in a seventh solvent, and then adding boron trifluoride ether complex dropwise to react to obtain compound X; Synthesis of compound III-1: The compound X reacts with biboric acid pinacol ester in an eighth solvent in the presence of a fourth base and a fourth catalyst to obtain compound III-1.

5. The method for preparing a helical chiral polycyclic aromatic hydrocarbon compound according to claim 2, wherein: When R stands for When, the structural formula of the compound III is shown in formula III-2: ; The synthesis steps of the compound III include: ； Synthesis of compound XIII: Compound XII is dissolved in a ninth solvent, maintained at a sixth temperature, and then an n-butyllithium solution is added dropwise thereto, stirred for reaction, and then compound XI is added and the temperature is raised to a seventh temperature with continuous stirring. After the reaction is complete, the reaction is quenched and the solvent is removed to obtain a second crude product. The second crude product is dissolved in a seventh solvent, and then boron trifluoride etherate and triethylsilane are added dropwise thereto for reaction to obtain compound XIII. Synthesis of compound III-2: The compound XIII is reacted with pinacol diborate in an eighth solvent in the presence of a fourth base and a fourth catalyst to obtain compound III-2.

6. An open-shell compound, characterized in that The open-shell compound is prepared by chemical oxidation of the helical chiral polycyclic aromatic hydrocarbon compound according to claim 1; The general structural formula of the open-shell compound is shown in Formula XIV: ； Wherein, R is selected from the following structures: 、 .

7. A method for preparing an open-shell compound according to claim 6, characterized in that: The steps include: ； Synthesis of compound XV: Under nitrogen atmosphere, compound I is dissolved in the tenth solvent, and n-butyl lithium is added dropwise to generate compound XV in situ; Synthesis of compound XIV: Iodine is added to the compound XV to generate compound XIV in situ.

8. Use of the helical chiral polycyclic aromatic hydrocarbon compound according to claim 1 or the open-shell compound according to claim 6 in the preparation of chemical sensors and photoelectric devices.

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