Preparation method of aza-heart cycloalkene near-infrared chiral luminescent material embedded with eight-membered ring

Abstract

The invention provides a preparation method of an eight-membered ring embedded aza-centered cycloalkene near-infrared chiral luminescent material, the eight-membered ring embedded aza-centered cycloalkene near-infrared chiral luminescent material comprises a chemical structure as shown in a formula (1) or a formula (2): # imgabs0 #, and R1, R2, R3 and R4 are respectively and independently selected from any one of H, C1-C20 alkyl, C1-C20 alkoxy and C6-C18 aryl. The material has good near-infrared chiral optical response, and enriches the types of cyclohexylene and near-infrared chiral optical materials.

Description

Technical Field

[0001] This application relates to the fields of organic synthesis and organic optoelectronic functional materials, and particularly to an eight-membered ring-embedded azacoronene-based near-infrared chiral luminescent material and a preparation method thereof. Background Art

[0002] As a new type of optical functional material, circularly polarized luminescence (CPL) materials exhibit important application values in the fields of 3D display, quantum communication, bioimaging, and CPL lasers. Near-infrared (NIR) materials have received extensive attention due to their unique optical properties, including deep tissue penetration ability, high quantum efficiency, excellent anti-scattering performance, and biological safety. However, the existing research on CPL materials mainly focuses on the visible light region, and there are still major technical challenges in the development of NIR-CPL materials.

[0003] Coronene, as a polycyclic aromatic hydrocarbon with a bowl-shaped structure, is an important structural unit of fullerenes. The optical properties of coronene can be effectively regulated by structural modification: on the one hand, introducing an eight-membered ring into the molecular skeleton can significantly change its configuration and electronic properties, and at the same time, the inherent structural distortion characteristics of the eight-membered ring can enhance the chiral stability of the molecule; on the other hand, heteroatom doping (such as pyrrole nitrogen atoms) can not only regulate the electronic structure of the molecule, but also realize the regulation of the oxidation state by using the electron-rich characteristics of pyrrole nitrogen, thereby expanding the optical response range of the material to the near-infrared region. However, the existing technology has not achieved the synergistic integration of nitrogen atom doping and eight-membered ring structure, which severely restricts the application and development of coronene-based materials in the field of NIR-CPL. Summary of the Invention

[0004] This application provides an eight-membered ring-embedded azacoronene-based near-infrared chiral luminescent material and a preparation method thereof, aiming to provide a material with good chiral optical response ranging to the near-infrared light region. The eight-membered ring-embedded azacoronene-based near-infrared chiral luminescent material enriches the types of coronene and near-infrared light chiral luminescent materials.

[0005] In the first aspect, an embodiment of this application proposes an eight-membered ring-embedded azacoronene-based near-infrared chiral luminescent material. The chiral azacoronene material embedded with an eight-membered ring includes the chemical structures shown in formula (1) or formula (2):

[0006]

[0007] Wherein, R 1 、R 2 、R 3 and R 4 are independently selected from H, C 1 -C 20 alkyl, C 1 -C20 Alkoxy group, C 6 -C 18 Any one of aryl groups. This type of material has good near-infrared chiral optical response. The azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring enriches the types of coronene and near-infrared chiral optical materials.

[0008] In some embodiments, the azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring includes one or more of the compounds shown in Formulas (3) to (14):

[0009]

[0010]

[0011] Among them, -OME represents -O-CH 3 , -tBU represents -C(CH 3 ) 3 .

[0012] In some embodiments, for the material shown in Formula (1), the circularly polarized emission optical response wavelength range is 600 - 850 nm; for the chemical structure shown in Formula (2), the circular dichroism optical response wavelength range is 350 - 1600 nm.

[0013] In some embodiments, in Formula (1), the R 1 is tert-butyl, R 2 and R 4 are methoxy groups, and R 3 is 2,4,6-trimethylphenyl.

[0014] In some embodiments, in Formula (2), the R 1 is tert-butyl, R 2 and R 4 are methoxy groups, and R 3 is 2,4,6-trimethylphenyl.

[0015] In a second aspect, an embodiment of the present application provides a preparation method of an azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring, including:

[0016] Under a protective atmosphere, at a temperature of 0 to 25 °C, the compound shown in Formula (H-2) undergoes a Scholl reaction in an organic solvent under the action of an oxidant to obtain the azacoronene-based near-infrared region I chiral luminescent material shown in Formula (4):

[0017]

[0018] In some embodiments, the preparation method further includes: under the condition that the temperature is 0 to 25 °C, subjecting the nitrogen heterohelicene-based near-infrared II chiral luminescent material with an embedded eight-membered ring shown in formula (4) to an oxidation reaction in an organic solvent under the action of an oxidant to obtain the nitrogen heterohelicene-based near-infrared II chiral luminescent material shown in formula (10);

[0019]

[0020] In some embodiments, the method further includes a post-treatment step, and the post-treatment step includes: sequentially adding triethylamine for quenching, extraction, drying, first filtration, concentrating under reduced pressure with the organic phase, separating by silica gel column chromatography, second concentration, second filtration, and drying to obtain the nitrogen heterohelicene-based near-infrared I chiral luminescent material with an embedded eight-membered ring.

[0021] In some embodiments, the preparation method of the compound shown in formula (H-2) includes: under heating conditions, mixing the compound shown in formula (H-4) and the compound shown in formula (H-3) to carry out a nucleophilic substitution reaction to obtain the compound shown in formula (H-2):

[0022]

[0023] In some embodiments, the preparation method of the compound shown in formula (H-4) includes: under heating conditions, mixing the compound shown in formula (H-5) with 3,6-diboron pinacol ester-9H-carbazole to carry out a palladium-catalyzed Suzuki coupling reaction to obtain the compound shown in formula (H-4);

[0024]

[0025] This application has at least the following beneficial effects:

[0026] For the nitrogen heterohelicene-based near-infrared chiral luminescent material with an embedded eight-membered ring according to the embodiments of the present application, using a nitrogen heterohelicene analogue with an embedded eight-membered ring as the core, the embedding of the eight-membered ring and the expansion of the π system endow the nitrogen heterohelicene with stable chirality and chiral optical response in the near-infrared I region; at the same time, the central pyrrole nitrogen atom is easily oxidized to form a stable radical with chiral optical response in the near-infrared II region, thereby obtaining a nitrogen heterohelicene-based chiral luminescent material with near-infrared response.

[0027] The distortion of the eight-membered ring structure can satisfy the resolution of chirality and the measurement of circular dichroism and circularly polarized luminescence spectra at room temperature conditions, and also lays a foundation for the preparation and application of near-infrared chiral luminescent materials. Description of the Drawings

[0028] Those skilled in the art will understand that the following drawings are for illustrative purposes only. It is expected that these drawings do not limit the scope of the present invention in any way.

[0029] Figure 1 The mass spectrometry detection result diagram of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in one embodiment is shown.

[0030] Figure 2 The hydrogen nuclear magnetic resonance spectrum diagram of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in one embodiment is shown.

[0031] Figure 3 The carbon nuclear magnetic resonance spectrum diagram of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in one embodiment is shown.

[0032] Figure 4 The single crystal structure diagram determined by X-ray diffractometer of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in one embodiment is shown.

[0033] Figure 5 The absorption and emission spectra of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in one embodiment are shown.

[0034] Figure 6 The circular dichroism spectrum diagram and circularly polarized luminescence performance diagram of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in one embodiment are shown.

[0035] Figure 7 The absorption spectrum of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in another embodiment is shown.

[0036] Figure 8 The circular dichroism spectrum diagram of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in another embodiment is shown.

[0037] Figure 9 The absorption asymmetry factor curve diagram of the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring in another embodiment is shown. Detailed implementation manners

[0038] The implementation manners of the present application will be further described in detail below in conjunction with the drawings and embodiments. The following detailed description of the embodiments and the drawings are used to exemplarily illustrate the principle of the present application, but cannot be used to limit the scope of the present application, that is, the present application is not limited to the described embodiments.

[0039] As used herein, "alkoxy" refers to -O-alkyl. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), tert-butoxy, and similar alkoxy groups.

[0040] As used herein, "alkyl" refers to a straight-chain or branched-chain saturated hydrocarbon group. Examples of alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl) and similar alkyl groups. In various embodiments, the alkyl group may contain from 1 to 20 carbon atoms, i.e., C 1-20 alkyl. In some embodiments, the alkyl group may contain from 1 to 6 carbon atoms and may be referred to as a "lower alkyl". Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and isopropyl), and butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl). In some embodiments, the alkyl group may be substituted as disclosed herein. The alkyl group is generally not substituted by another alkyl group, alkenyl group or alkynyl group.

[0041] Throughout this specification, substituents of compounds are disclosed in groups or ranges. It is expressly contemplated that such a description includes every individual sub-combination of the members of these groups and ranges. For example, it is expressly contemplated that the term "C1-20 alkyl" discloses individually C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C1-C20, C1-C19, C1-C18, C1-C17, C1-C16, C1-C15, C1-C14, C1-C13, C1-C12, C1-C11, C1-C10, C1-C9, C1-C8, C1-C7, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C20, C2-C19, C2-C18, C2-C17, C2-C16, C2-C15, C2-C14, C2-C13, C2-C12, C2-C11, C2-C10, C2-C9, C2-C8, C2-C7, C2-C6, C2-C5, C2-C4, C2-C3, C3-C20, C3-C19, C3-C18, C3-C17, C3-C16, C3-C15, C3-C14, C3-C13, C3-C12, C3-C11, C3-C10, C3-C9, C3-C8, C3-C7, C3-C6, C3-C5, C3-C4, C4-C20, C4-C19, C4-C18, C4-C17, C4-C16, C4-C15, C4-C14, C4-C13, C4-C12, C4-C11, C4-C10, C4-C9, C4-C8, C4-C7, C4-C6, C4-C5, C5-C20, C5-C19, C5-C18, C5-C17, C5-C16, C5-C15, C5-C14, C5-C13, C5-C12, C5-C11, C5-C10, C5-C9, C5-C8, C5-C7, C5-C6, C6-C20, C6-C19, C6-C18, C6-C17, C6-C16, C6-C15, C6-C14, C6-C13, C6-C12, C6-C11, C6-C10, C6-C9, C6-C8, C6-C7, C7-C20, C7-C19, C7-C18, C7-C17, C7-C16, C7-C15, C7-C14, C7-C13, C7-C12, C7-C11, C7-C10, C7-C9, C7-C8, C8-C20, C8-C19, C8-C18, C8-C17, C8-C16, C8-C15, C8-C14, C8-C13, C8-C12, C8-C11, C8-C10, C8-C9, C9-C20, C9-C19,C9-C18, C9-C17, C9-C16, C9-C15, C9-C14, C9-C13, C9-C12, C9-C11, C9-C10, C10-C20, C10-C19, C10-C18, C10-C17, C10-C16, C10-C15, C10-C14, C10-C13, C10-C12, C10-C11, C11-C20, C11-C19, C11-C18, C11-C17, C11-C16, C11-C15, C11-C14, C11-C13, C11-C12, C12-C20, C12-C19, C12-C18, C12-C17, C12-C16, C12-C15, C12-C14, C12-C13, C13-C20, C13-C19, C13-C18, C13-C17, C13-C16, C13-C15, C13-C14, C14-C20, C14-C19, C14-C18, C14-C17, C14-C16, C14-C15, C15-C20, C15-C19, C15-C18, C15-C17, C15-C16, C16-C20, C16-C19, C16-C18, C16-C17, C17-C20, C17-C19, C17-C18, C18-C20, C18-C19, C19-C20 alkyl. As other examples, integers in the range from 0 to 12 are explicitly expected to disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 individually; integers in the range from 1 to 20 are explicitly expected to disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 individually.

[0042] As used herein, "aryl" refers to an aromatic monocyclic hydrocarbon ring system or polycyclic system, and the aryl may contain 6 to 16 carbon atoms in its ring system, which may include multiple fused rings. In some embodiments, the polycyclic aryl may contain 7 to 16 carbon atoms. The aryl may be covalently linked to a defined chemical structure at any suitable ring position, which forms a stable structure. Examples of aryls containing only aromatic carbocyclic rings include, but are not limited to, phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthryl (tricyclic), phenanthryl (tricyclic), and similar aryls. Examples of polycyclic systems in which at least one aromatic carbocyclic ring is linked to one or more cycloalkyls include (but are not limited to) benzo derivatives of cyclopentane (i.e., indanyl, which is a 5,6-bicyclic cycloalkyl / aromatic ring system), cyclohexane (i.e., tetrahydronaphthyl, which is a 6,6-bicyclic cycloalkyl / aromatic ring system). In some embodiments, the aryl may be substituted as disclosed herein. In certain embodiments, the aryl is substituted by another aryl and may be referred to as a biaryl. Each aryl in the biaryl may be substituted as disclosed herein.

[0043] Throughout this application, temperatures are disclosed in ranges. It is specifically contemplated that such description includes narrower temperature ranges within these ranges, as well as the maximum and minimum temperatures of these temperature ranges.

[0044] Throughout the specification, structures may or may not be represented by chemical names. When any questions arise regarding nomenclature, the structure shall prevail.

[0045] In a first aspect, an embodiment of the present application provides a nitrogen-containing azacoronene-based near-infrared chiral luminescent material embedded with an eight-membered ring. The chiral azacoronene material embedded with an eight-membered ring includes a chemical structure represented by Formula (1) or Formula (2):

[0046]

[0047] Wherein, R 1 , R 2 , R 3 and R 4 are each independently selected from any one of H, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 6 -C 18 aryl. Such materials have good near-infrared chiral optical responses, and the nitrogen-containing azacoronene-based near-infrared chiral luminescent materials embedded with an eight-membered ring enrich the types of coronenes and near-infrared chiral optical materials.

[0048] According to the embodiments of the present application, the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring uses a nitrogen-containing core annulene analogue with an embedded eight-membered ring as the core. The embedding of the eight-membered ring and the expansion of the π system endow the nitrogen-containing core annulene with stable chirality and chiral optical response in the first near-infrared region. In addition, pyrrole nitrogen atoms are doped in the core annulene, and radicals are formed by oxidation using the electron-rich characteristics of the pyrrole nitrogen atoms. Thus, the radicals have the characteristics of chiral optical response in the second near-infrared region, and a nitrogen-containing core annulene-based chiral luminescent material with near-infrared response is obtained.

[0049] Solubilizing groups such as C 1 -C 20 alkyl, C 1 -C 20 alkoxy, and C 6 -C 18 aryl are introduced on the periphery of the material, which can endow the material with good solubility and processability in common organic solvents.

[0050] The substituents in the eight-membered ring bay region of the material, that is, the two benzene rings containing R 4 , due to the steric hindrance effect, enhance the chiral stability, can meet the chiral resolution and the measurement of circular dichroism spectrum and circularly polarized luminescence spectrum at room temperature, and also lay a foundation for the preparation and application of near-infrared chiral luminescent materials.

[0051] In summary, this type of material has good near-infrared chiral optical response. The nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring enriches the types of core annulene and near-infrared chiral optical materials.

[0052] In some embodiments, the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring includes one or more of the compounds shown in Formula (3) to Formula (14):

[0053]

[0054] Among them, -OME represents -O-CH 3 , and -tBU represents -C(CH 3 ) 3 .

[0055] In some embodiments, the circularly polarized emission optical response wavelength range of the material shown in Formula (1) is 600 - 850 nm. This wavelength range covers part of the visible light region, and the chiral optical material can be used to manufacture display devices with special optical properties. The chiral optical material has a selective response to light with a specific polarization state and can be used to manufacture highly sensitive photodetectors, etc.

[0056] In some embodiments, the circular dichroism optical response wavelength range of the chemical structure shown in formula (2) is 350 - 1600 nm. Thus, the wavelength range covers the ultraviolet to near-infrared region, enabling the combination of multiple imaging techniques, and the chiral optical properties of the material can be utilized to achieve the regulation of infrared light.

[0057] In some embodiments, in formula (1), the R 1 is tert-butyl, R 2 and R 4 are methoxy, and R 3 is 2,4,6-trimethylphenyl. Thus, the circularly polarized emission optical response of the material shown in formula (1) has a maximum emission dissymmetry factor of 0.0013 at 715 nm.

[0058] In some embodiments, in formula (2), the R 1 is tert-butyl, R 2 and R 4 are methoxy, and R 3 is 2,4,6-trimethylphenyl. Thus, the circular dichroism optical response of the material shown in formula (2) has a maximum absorption dissymmetry factor of 0.0029 at 1119 nm.

[0059] Second, the embodiments of the present application provide a preparation method of an octacyclic-ring-embedded azacoronene-based near-infrared chiral luminescent material, including:

[0060] Under a protective atmosphere and at a temperature of 0 to 25 °C, the compound shown in formula (H-2) undergoes a Scholl reaction in an organic solvent under the action of an oxidant to obtain the octacyclic-ring-embedded azacoronene-based near-infrared region I chiral luminescent material shown in formula (4);

[0061]

[0062] In some embodiments, the preparation method includes: under a protective atmosphere of nitrogen or argon and at a temperature of 0 to 25 °C, the compound shown in formula (H-2) undergoes a Scholl reaction in dichloromethane under the action of the oxidants 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and trifluoromethanesulfonic acid to obtain the octacyclic-ring-embedded azacoronene-based near-infrared region I chiral luminescent material shown in formula (4);

[0063]

[0064] In some embodiments, the preparation method further includes: under the condition that the temperature is 0 to 25 °C, subjecting the near-infrared region II chiral luminescent material of azacoronene with an embedded eight-membered ring shown in formula (4) to an oxidation reaction in an organic solvent under the action of an oxidant to obtain the near-infrared region II chiral luminescent material of azacoronene with an embedded eight-membered ring shown in formula (10);

[0065]

[0066] In some embodiments, the preparation method further includes: under the condition that the temperature is 0 to 25 °C, subjecting the near-infrared region II chiral luminescent material of azacoronene with an embedded eight-membered ring shown in formula (4) to an oxidation reaction in an organic solvent under the action of an oxidant nitrous hexafluoroantimonate to obtain the near-infrared region II chiral luminescent material of azacoronene with an embedded eight-membered ring shown in formula (10);

[0067]

[0068] In some embodiments, the method further includes a post-treatment step, and the post-treatment step includes: sequentially adding triethylamine for quenching, extraction, drying, first filtration, concentrating the organic phase under reduced pressure, separating by silica gel column chromatography, second concentration, second filtration, and drying to obtain the near-infrared region I chiral luminescent material of azacoronene with an embedded eight-membered ring.

[0069] This step specifically includes: weighing the compound shown in formula (H-2) and 2,3-dichloro-5,6-dicyanobenzoquinone and adding them to a 100 mL reaction eggplant flask, adding anhydrous dichloromethane and stirring until dissolved clearly, protecting with nitrogen, and dropwise adding trifluoromethanesulfonic acid at 0 °C for reaction. Subsequently, triethylamine is added for quenching, extracted 3 times with water and dichloromethane, dried with anhydrous magnesium sulfate, filtered, the organic phase is concentrated under reduced pressure, separated by silica gel column chromatography using petroleum ether and dichloromethane as the mobile phase, concentrated, filtered, and dried to obtain the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring.

[0070] In some embodiments, the preparation method of the compound shown in formula (H-2) includes: under heating conditions, mixing the compound shown in formula (H-4) and the compound shown in formula (H-3) to carry out a nucleophilic substitution reaction to obtain the compound shown in formula (H-2):

[0071]

[0072] In some embodiments, the preparation method of the compound shown in formula (H-2) includes: under heating conditions, mixing the compound shown in formula (H-4) and the compound shown in formula (H-3) in an organic solvent under the action of cesium carbonate to carry out a nucleophilic substitution reaction to obtain the compound shown in formula (H-2):

[0073]

[0074] This step specifically includes: weighing the compound shown in formula (H-4) and cesium carbonate and adding them to a reaction eggplant flask, adding anhydrous N,N-dimethylformamide, stirring at room temperature for 1 hour under nitrogen protection, then adding the compound shown in formula (H-3), and reacting at 160 °C for 12 hours. Cool to room temperature, extract with water and dichloromethane, dry with anhydrous magnesium sulfate, filter by suction, concentrate the organic phase under reduced pressure, perform silica gel column chromatography separation using petroleum ether and ethyl acetate as the mobile phase, concentrate, filter by suction, and dry to obtain a white solid, namely the compound shown in formula (H-2).

[0075] In some embodiments, the preparation method of the compound shown in formula (H-4) includes: under heating conditions, mixing the compound shown in formula (H-5) with 3,6-diboronopinanediol ester-9H-carbazole to carry out a palladium-catalyzed Suzuki coupling reaction to obtain the compound shown in formula (H-4):

[0076]

[0077] In some embodiments, the compound shown in formula (H-5) and 3,6-diboronopinanediol ester-9H-carbazole are mixed in a mixed solvent containing cesium carbonate, and a Suzuki coupling reaction is carried out under the action of the catalyst tetrakis(triphenylphosphine)palladium. The mixed solvent includes 1,4-dioxane and water to obtain the compound shown in formula (H-4):

[0078]

[0079] This step specifically includes: weighing 3,6-diboronopinanediol ester-9H-carbazole, the compound shown in formula (H-5), cesium carbonate and tetrakis(triphenylphosphine)palladium and adding them to a reaction flask, and adding 1,4-dioxane and water, reacting at 100 °C for 12 hours under nitrogen protection. Cool to room temperature, extract with dichloromethane and water, collect the organic phase, dry with anhydrous magnesium sulfate, filter by suction, concentrate under reduced pressure, perform silica gel column chromatography separation using petroleum ether and ethyl acetate as the mobile phase, concentrate, filter by suction, and dry to obtain a white solid, namely the compound shown in formula (H-4).

[0080] Examples

[0081] The following examples more specifically describe the content disclosed in the present application. These examples are only for illustrative purposes, because various modifications and changes within the scope of the content disclosed in the present application are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on mass, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are all commercially available.

[0082] Example 1

[0083] This example provides a method for preparing a nitrogen-containing core annulene-based near-infrared chiral luminescent material embedded with an eight-membered ring, including:

[0084]

[0085] Synthesis of the compound shown in formula (H-4): Weigh 3,6-diboron pinacol ester-9H-carbazole (1.26 g, 3.00 mmol), compound 5 (1.92 g, 3.60 mmol), cesium carbonate (2.44 g, 7.50 mmol) and tetrakis(triphenylphosphine)palladium (173.4 mg, 0.15 mmol) and add them to a 100 mL reaction flask. Then add 1,4-dioxane (30 mL) and water (6 mL). React at 100 °C for 12 hours under nitrogen protection. Cool to room temperature, extract 3 times with dichloromethane (30 mL) and water (30 mL), collect the organic phase, dry it over anhydrous magnesium sulfate, filter by suction, concentrate under reduced pressure, perform silica gel column chromatography separation using petroleum ether and ethyl acetate (2 / 1, v / v) as the mobile phase, concentrate, filter by suction, and dry in an oven to obtain a white solid, which is the compound shown in formula (H-4). The obtained mass is 2.25 g, and the yield is 77%.

[0086] The NMR characterization results of the compound shown in formula (H-4) are as follows:

[0087] 1 H NMR(850MHz,CD 2 Cl 2 )δ8.03(s,1H),7.49(s,4H),7.40(s,2H),7.12(d,J=8.2Hz,2H),6.94–6.87(m,6H),6.76(d,J=8.3Hz,4H),6.34(s,4H),3.74(s,12H),3.10(s,12H),1.46(s,18H)ppm. 13 C NMR(214MHz,CD 2 Cl 2 )δ150.07,147.71,147.30,141.61,137.91,136.83,135.14,131.53,129.27,126.22,122.95,122.59,121.51,114.11,110.62,109.56,55.48,54.79,34.55,31.18ppm.

[0088] Synthesis of the compound represented by formula (H-2): Weigh the compound represented by formula (H-4) (976 mg, 1.00 mmol) and cesium carbonate (652 mg, 2.00 mmol) and add them to a 100 mL reaction flask. Then add anhydrous N,N-dimethylformamide (10 mL), stir at room temperature for 1 hour under nitrogen protection, and then add compound 3 (346 mg, 1.10 mmol). React at 160 °C for 12 hours. Cool to room temperature, extract 3 times with water (50 mL) and dichloromethane (50 mL), dry with anhydrous magnesium sulfate, filter by suction, concentrate the organic phase under reduced pressure, perform silica gel column chromatography separation using petroleum ether and ethyl acetate (2 / 1, v / v) as the mobile phase, concentrate, filter by suction, and dry to obtain a white solid, which is the compound represented by formula (H-2). The obtained mass is 915 mg and the yield is 72%.

[0089] The calculation method of this yield is: the ratio of the amount of the target product actually obtained to the amount of the product that should be obtained in a complete reaction theoretically. The amount of the product that should be obtained in a complete reaction theoretically is calculated based on the reaction raw materials. Here, the compound represented by formula (H-2) is used as the raw material for calculation.

[0090] The NMR characterization results of the compound represented by formula (H-2) are as follows:

[0091] 1 H NMR(850MHz,CD 2 Cl 2 )δ7.63–7.61(m,4H),7.53(s,4H),7.42–7.40(m,4H),7.19(s,2H),7.08–7.06(m,2H),7.00(d,J=10.2Hz,4H),6.83-6.81(m,6H),6.48(d,J=8.3Hz,2H),6.35(d,J=2.0Hz,4H),3.78(s,12H),3.19(s,12H),2.51(s,3H),1.81(s,6H),1.48(s,18H)ppm. 13 C NMR(214MHz,CD 2 Cl 2)δ 150.30, 147.79, 147.40, 141.56, 140.91, 138.16, 137.66, 137.35, 136.66, 135.00, 133.89, 132.32, 130.29, 129.59, 128.33, 127.76, 126.80, 126.71, 126.24, 126.02, 123.36, 123.10, 122.42, 121.48, 114.23, 110.74, 109.30, 55.52, 54.91, 34.59, 31.19, 20.96, 19.72 ppm.

[0092] Synthesis of the nitrogen heterohelicene - type near - infrared chiral luminescent material with an embedded eight - membered ring shown in formula (4): Weigh the compound shown in formula (H - 2) (100 mg, 0.079 mmol) and 2,3 - dichloro - 5,6 - dicyanobenzoquinone (357 mg, 1.57 mmol) and add them to a 100 mL reaction flask. Add anhydrous dichloromethane (50 mL) and stir until clear. Under nitrogen protection, slowly add trifluoromethanesulfonic acid (0.5 mL) dropwise at 0 °C and react for 0.5 hours. Add triethylamine (3 mL) to quench the reaction. Extract with water (50 mL) and dichloromethane (50 mL) three times, dry with anhydrous magnesium sulfate, filter by suction, concentrate the organic phase under reduced pressure, perform silica gel column chromatography separation with petroleum ether and ethyl acetate (2 / 1, v / v) as the mobile phase, concentrate, filter by suction, and dry in an oven to obtain a green solid, which is the nitrogen heterohelicene - type near - infrared chiral luminescent material with an embedded eight - membered ring shown in formula (4). The obtained mass is 63 mg and the yield is 64%, that is, the nitrogen heterohelicene - type near - infrared chiral luminescent material with an embedded eight - membered ring shown in formula (4).

[0093] The NMR characterization results of the nitrogen heterohelicene - type near - infrared chiral luminescent material with an embedded eight - membered ring shown in formula (4) are as follows:

[0094] 1 H NMR (850 MHz, CD 2 Cl 2 )δ 9.81 (d, J = 9.1 Hz, 2H), 9.16 (s, 2H), 8.91 (s, 2H), 8.90 (s, 2H), 8.19 (s, 2H), 7.79 (d, J = 9.1 Hz, 2H), 7.28 (s, 2H), 4.44 (s, 6H), 4.26 (s, 6H), 4.11 (s, 6H), 3.42 (s, 6H), 2.56 (s, 3H), 2.05 (s, 6H), 1.83 (s, 18H) ppm. 13 C NMR (214 MHz, CD 2 Cl 2)δ 153.83, 152.66, 152.22, 148.80, 147.30, 138.33, 137.43, 133.56, 130.57, 130.19, 130.00, 129.90, 129.73, 129.65, 129.29, 128.99, 128.63, 128.59, 128.13, 127.58, 125.02, 124.20, 124.08, 123.71, 122.31, 121.55, 121.53, 119.67, 118.32, 118.28, 115.82, 115.65, 112.63, 106.40, 105.60, 61.71, 60.39, 56.85, 56.10, 35.69, 31.83, 29.68, 19.92 ppm.

[0095] Example 2

[0096] This example provides a method for chiral resolution of a near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring, including:

[0097]

[0098] Perform chiral resolution on the near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring shown in formula (4) by high-performance liquid chromatography equipped with a Daicel Chiralpak IE chiral column (250×4.6 mm i.d), with dichloromethane as the mobile phase, a flow rate of 0.8 mL / min, and a detection wavelength of 639 nm. The enantiomers 1-P and 1-M are obtained, and the e.e. is greater than 99%.

[0099] e.e. is the abbreviation of "Enantiomeric Excess". It is an index used to measure the relative content between a pair of enantiomers in a chiral compound.

[0100] Example 3

[0101] This example provides a method for preparing a racemate of a near-infrared chiral luminescent material of azacoronene with an embedded eight-membered ring shown in formula (10), specifically including the following steps:

[0102]

[0103] Weigh the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4) prepared in Example 1 (3 mg, 2.4 μmol) and nitrous acid hexafluoroantimonate (0.64 mg, 2.4 μmol), add them to a 50 mL reaction eggplant flask, add anhydrous dichloromethane (20 mL), stir to dissolve clearly, protect with nitrogen, stir and react at room temperature for 0.5 hour, concentrate, filter by suction, and obtain brownish solid 1 ·+ , with a mass of 3 mg and a yield of 84%, that is, the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10).

[0104] Example 4

[0105] This example provides a preparation method for a chiral pure nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring, which specifically includes the following steps:

[0106]

[0107] Using chiral pure enantiomers 1-P and 1-M as raw materials, weigh 0.5 mg of 1-P and 1-M prepared in Example 2 respectively. After dissolving them with 5 mL of dichloromethane, add 1 equivalent of nitrous acid hexafluoroantimonate to 1-P and 1-M respectively, and stir at room temperature for 30 min to obtain chiral pure 1 ·+ -P and 1 ·+ -M.

[0108] Structure and performance test

[0109] Perform the following tests on the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring prepared in the example.

[0110] 1. Mass spectrometry test of the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4):

[0111] Determine the molecular weight by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (the matrix is DCTB), and the test results are as Figure 1 shown. It can be Figure 1 seen that the experimentally measured molecular weight is consistent with the target molecular weight, and the isotope distribution is completely consistent with the calculated simulation.

[0112] 2. NMR test of the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4):

[0113] Characterize the hydrogen spectrum and carbon spectrum of this material using a Bruker Ascend nuclear magnetic resonance spectrometer (850 MHz), and the results are as Figure 2 and Figure 3 shown. After analysis, it can be seen that the integral number of hydrogen atoms and the types of hydrogen and carbon are all consistent with the target product.

[0114] 3. Single crystal structure characterization of the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4)

[0115] Cultivation of the single crystal of this material: Weigh 1 mg of the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4) of the above example and dissolve it in 2 mL of dichloromethane solution. Filter it through a 0.45 μm organic filter membrane into a 5 mL sample bottle, and then put it into a sample bottle containing methanol solution. After sealing and standing for 48 h, green block-shaped single crystals are obtained. The single crystal structure is determined by an X-ray diffractometer, as Figure 4 shown. The crystal data are as follows:

[0116] Monoclinic system, space group P21 / c (No. 14), a = 18.9661(19) Å, b = 17.4437(13) Å, c = 22.8561(18) Å, β = 101.863(10)°, unit cell volume V = 7400.2(11) Å3, Z = 4, temperature T = 100.15 K, absorption coefficient μ(CuKα) of copper Kα radiation = 0.566 mm-1, calculated density Dcalc = 1.125 g / cm3. 38712 diffraction points are measured (6.426° ≤ 2Θ ≤ 125.972°), among which 11421 are independent diffraction points (internal standard deviation Rint = 0.0890, sigma deviation Rsigma = 0.0989). All calculations use these independent diffraction points. Finally, for diffraction points with I > 2σ(I), the R 1 factor is 0.1059, and for all data, the wR 2 factor is 0.3268.

[0117] Cultivation of the single crystal of the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10) prepared in Example 3: Weigh 1 mg of the nitrogen-containing core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10) prepared in Example 3 above and dissolve it in 2 mL of dichloromethane solution. Filter it through a 0.45 μm organic filter membrane into a 5 mL sample bottle, and then put it into a sample bottle containing methanol solution. After sealing and standing for 72 h, brownish-black block-shaped single crystals are obtained. The single crystal structure is determined by an X-ray diffractometer, as Figure 4 shown. The crystal data are as follows:

[0118] Triclinic system, space group P-1 (No. 2), a = 18.1110(8) Å, b = 19.2209(8) Å, c = 24.7429(10) Å, α = 76.015(4)°, β = 69.217(4)°, γ = 74.711(4)°, unit cell volume V = 7662.3(6) ų, Z = 2, temperature T = 100.00(10) Kelvin, absorption coefficient μ of copper Kα radiation = 3.443 mm⁻¹, calculated density Dcalc = 1.289 g / cm³. A total of 100174 diffraction points were measured (5.674° ≤ 2Θ ≤ 144.044°), among which there were 28414 independent diffraction points (internal standard deviation Rint = 0.0661, sigma deviation Rsigma = 0.0575), and all calculations were performed using these independent diffraction points. Finally, for diffraction points with I > 2σ(I), the R 1 factor is 0.1277, and for all data, the wR 2 factor is 0.3050.

[0119] Figure 4 Among them, a is the single crystal structure of the azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4); b is the single crystal structure of its oxidation product formula (10).

[0120] It can be seen from Figure 4 the single crystal structure of the azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring that the azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4) and its oxidation product formula (10) were successfully prepared.

[0121] 4. Characterization of the emission spectra of the azacoronene-based near-infrared chiral luminescent materials shown in formula (4) and formula (10)

[0122] Weigh 1 mg of the azacoronene-based near-infrared chiral luminescent material shown in formula (4) of Example 1 above, dissolve it in dichloromethane solution, and use an ultraviolet-visible-near-infrared spectrophotometer and a steady-state transient near-infrared fluorescence spectrometer to measure its liquid-phase absorption and fluorescence emission spectra. The test results are as Figure 5 shown.

[0123] Figure 5 are the absorption and emission spectra of the azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4). It can be seen from Figure 5 that the maximum absorption wavelength of the azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4) is 639 nm, the maximum emission is 652 nm, and the Stokes shift is only 13 nm. And it has deep red narrow-band emission, the full width at half maximum is 28 nm, and the fluorescence quantum yield is 31%.

[0124] Weigh 1 mg of the nitrogen hetero-core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10) of Example 3 above, dissolve it in dichloromethane solution, and use a UV-Vis-NIR spectrophotometer to measure its liquid-phase absorption spectrum. The test results are as Figure 7 shown.

[0125] Figure 7 The absorption spectrum of the material shown in formula (10). As Figure 7 known, the absorption spectrum of the nitrogen hetero-core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10) reaches the second near-infrared region, and the maximum absorption wavelength is 1119 nm. Its absorption in the second near-infrared region has potential application value in biological imaging and photothermal therapy for tumors.

[0126] 5. Circular dichroism spectra and circularly polarized emission spectra of the materials shown in formula (4) and formula (10). Characterization of the circular dichroism spectra and circularly polarized luminescence properties of the nitrogen hetero-core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring

[0127] Use a JASCO J-1700 circular dichroism spectrometer and a JASCO CPL-300 to characterize the circular dichroism spectrum and circularly polarized emission spectrum of the nitrogen hetero-core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4). The results are as Figure 6 shown, where 1-P and 1-M represent the enantiomers 1-P and 1-M corresponding to the nitrogen hetero-core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (4) in sequence. As Figure 6 known, the circular dichroism spectrum and circularly polarized emission spectrum of this material are both mirror-symmetric. This material has circular dichroism signals in the range of 300 - 680 nm, and the Cotton coefficient is the largest at 458 nm, which is 103 M -1. cm -1 , and its absorption asymmetry factor is the largest at 450 nm, which is 0.0047. This material has circularly polarized luminescence in the range of 600 - 850 nm, and it has a near-infrared circularly polarized luminescence response. The emission asymmetry factor is the largest at 715 nm, which is 0.0013.

[0128] Use a JASCO J-1700 circular dichroism spectrometer to characterize the circular dichroism spectrum of the nitrogen hetero-core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10). The results are as Figure 8 and Figure 9 shown, where 1 ·+ -P and 1 ·+ -M represent the enantiomers 1 ·+ -P and 1 ·+ -M corresponding to the nitrogen hetero-core annulene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10) in sequence. As Figure 8It is known that the chiral optical response range of the azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring shown in formula (10) can reach 350 nm - 1600 nm, reaching the second near-infrared region, and having an extremely strong chiral optical response in the second near-infrared region. From Figure 9 It is known that its absorption asymmetry factor is maximally 0.0029 at 1119 nm.

[0129] In summary, the present invention has for the first time prepared an azacoronene-based near-infrared chiral luminescent material with an embedded eight-membered ring, which has a chiral optical response in the near-infrared region, still retains chirality after oxidation, and also has an extremely strong chiral optical response in the second near-infrared region, laying a foundation for the preparation and application of chiral optical devices and near-infrared region II bioimaging materials in the second near-infrared region.

[0130] Although the present application has been described with reference to the preferred embodiments, various improvements can be made to it and the groups therein can be replaced with equivalents without departing from the scope of the present application. In particular, as long as there is no structural conflict, the technical features mentioned in each embodiment can be combined in any way. The present application is not limited to the specific embodiments disclosed in the text, but includes all technical solutions falling within the scope of the claims.

Claims

1. A near-infrared chiral luminescent material of nitrogen-centered cycloolefin with an embedded eight-membered ring, characterized in that: The chiral nitrogen-centered cycloolefin material with an embedded eight-membered ring comprises a chemical structure shown in formula (1) or formula (2): Wherein, R1, R2, R3 and R4 are independently selected from H, C1-C 20 Alkyl, C1-C 20 Alkoxy, C6-C 18 Any one of the aromatic groups. This type of material has a good near-infrared chiral optical response, and the nitrogen-containing cyclopentene near-infrared chiral luminescent material with an embedded eight-membered ring enriches the types of cyclopentene and near-infrared chiral optical materials.

2. The near-infrared chiral luminescent material of nitrogen-centered cycloolefins with an embedded eight-membered ring according to claim 1, characterized in that: The nitrogen-centered cycloolefin near-infrared chiral luminescent material with an embedded eight-membered ring includes one or more of the compounds represented by formula (3) to formula (14): Among them, -OME represents -O-CH3, and -tBU represents -C(CH3)3.

3. The near-infrared chiral luminescent material of nitrogen-centered cycloolefins with an embedded eight-membered ring according to claim 1, characterized in that: The circular polarization emission optical response wavelength range of the material shown in formula (1) is 600-850nm; the circular dichroism optical response wavelength range of the chemical structure shown in formula (2) is 350-1600nm.

4. The near-infrared chiral luminescent material of nitrogen-centered cycloolefins with an embedded eight-membered ring according to claim 1, characterized in that: In formula (1), R1 is tert-butyl, R2 and R4 are methoxy, and R3 is 2,4,6-trimethylphenyl.

5. The near-infrared chiral luminescent material of nitrogen-centered cycloolefins with an embedded eight-membered ring according to claim 1, characterized in that: In formula (2), R1 is tert-butyl, R2 and R4 are methoxy, and R3 is 2,4,6-trimethylphenyl.

6. A method for preparing an octahedral nitrogen-centered cycloolefin near-infrared chiral luminescent material as described in any one of 1 to 5, characterized in that: The preparation method comprises: in a protective atmosphere and at a temperature of 0 to 25° C., subjecting the compound represented by formula (H-2) to a Scholle reaction in an organic solvent under the action of an oxidant to obtain a near-infrared first-zone chiral luminescent material of the nitrogen-centered cycloolefin type with an embedded eight-membered ring represented by formula (4):

7. The preparation method according to claim 6, characterized in that: The preparation method further comprises: subjecting the nitrogen-centered cycloolefin near-infrared second-zone chiral luminescent material with an embedded eight-membered ring as shown in formula (4) to an oxidation reaction in an organic solvent under the action of an oxidant at a temperature of 0 to 25° C. to obtain the nitrogen-centered cycloolefin near-infrared second-zone chiral luminescent material with an embedded eight-membered ring as shown in formula (10); 8. The preparation method according to claim 6 or 7, characterized in that: The method also includes a post-processing step, which includes: sequentially adding triethylamine for quenching, extraction, drying, first suction filtration, concentrating the organic phase under reduced pressure, silica gel column chromatography separation, second concentration, second suction filtration, and drying to obtain the nitrogen-centered cycloolefin near-infrared first-zone chiral luminescent material with an embedded eight-membered ring.

9. The preparation method according to claim 6, characterized in that: The preparation method of the compound represented by formula (H-2) comprises: mixing the compound represented by formula (H-4) and the compound represented by formula (H-3) under heating conditions to carry out a nucleophilic substitution reaction to obtain the compound represented by formula (H-2):

10. The preparation method according to claim 9, characterized in that: The preparation method of the compound represented by formula (H-4) comprises: mixing the compound represented by formula (H-5) with 3,6-diboronic acid pinacol ester-9H-carbazole under heating conditions to carry out a palladium-catalyzed Suzuki coupling reaction to obtain the compound represented by formula (H-4):

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