Structure and uses of a class of benzisoindole dimers

Abstract

This application discloses a compound of formula (I), and its tautomers, polymorphs, solvates, or salts thereof. The compound provided in this application is a novel fluorescent material with a benzisoindole dimer framework.

Description

Technical Field

[0001] This application belongs to the field of organic fluorescent materials and relates to a class of luminescent core materials with a novel structure of benzeneisoindole dimer compounds. Background Technology

[0002] In the field of luminescence, the study of organic materials is receiving increasing attention. This is because organic compounds are diverse, highly tunable, rich in color, high in color purity, and relatively flexible in molecular design. Based on different molecular structures, organic luminescent materials can be divided into: (1) organic small molecule luminescent materials; (2) organic polymer luminescent materials; and (3) organic complex luminescent materials. These luminescent materials each have their own characteristics in terms of luminescence mechanism, physicochemical properties, and applications.

[0003] Organic small-molecule luminescent materials are diverse, often possessing conjugated heterocycles and various chromophores. Their structures are easily modulated, and their conjugation length can be altered by introducing unsaturated groups such as alkene bonds and benzene rings, thereby changing the photoelectric properties of the compounds. Common organic luminescent materials include diazoles and their derivatives, triazoles and their derivatives, fluorescein / rhodamine and their derivatives, coumarin derivatives, Cy series cyanine dyes, 1,8-naphthalimide derivatives, pyrazoline derivatives, triphenylamine derivatives, porphyrin compounds, carbazole, pyrazine, thiazole derivatives, and perylene derivatives. However, existing fluorescent materials are gradually failing to meet the growing demand, and traditional small-molecule fluorescent materials are prone to fluorescence quenching in the solid state. Devices fabricated using conventional doping methods are also prone to aggregation and crystallization, leading to reduced device lifetime. Therefore, artificially creating a class of fluorescent materials with novel frameworks is of great significance. New frameworks can functionally expand new properties, potentially complementing existing compounds and greatly expanding the structure and function of fluorescent materials. Summary of the Invention

[0004] According to one aspect of this application, a compound of formula (I), its tautomers, polymorphs, solvates, or salts thereof, and a method for preparing the same are provided. The compound exhibits excellent fluorescence properties.

[0005] Compounds represented by formula (I), and their tautomers, polymorphs, solvates, or salts thereof,

[0006]

[0007] in,

[0008] X and Y are independently selected from nitrogen, phosphorus, arsenic, tellurium, and boron atoms;

[0009] R 1 R 4Same or different; R 1 R 4 Independently selected from hydrogen, C1–C 30 Alkyl, substituted C1–C 30 Alkyl, C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 Heteroaryl, phosphinyl, substituted phosphinyl, boryl, substituted boryl, silyl, substituted silyl, halogen, amino, substituted amino, and optionally heteroatom groups selected from the following: CO, O, S, SO, SO2, NR. a -N=, =N-;

[0010] R 2 R 5 Same or different; R 2 R 5 Independently selected from C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 Mixed aromatics;

[0011] R 3 R 6 Same or different; R 7 R 8 Same or different; R 3 R 6 R 7 R 8 Independently selected from hydrogen atoms, C1–C 30 Alkyl, substituted C1–C 30 Alkyl, C1–C 30 Alkenyl, substituted C1–C 30 alkenyl, C1–C 30 Alkyne group, substituted C1–C 30 alkynyl group, C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 heteroaryl, C1–C 30 cycloalkyl, substituted C1–C 30 cycloalkyl, C1–C 30 Heterocyclic alkyl, substituted C1–C 30 Heterocyclic alkyl, phosphinyl, halogen, silyl, boronyl, germanium, arsenic, selenium, and optionally heteroatom groups selected from the following: CO, O, S, SO, SO2, NR are inserted at any position. a-N=, =N-;

[0012] R a It is independently selected from H, alkyl or aryl.

[0013] Optionally, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 It is independently selected from H atoms, aryl groups, substituted aryl groups, heteroaryl groups, and substituted heteroaryl groups.

[0014] Optionally, both X and Y are N.

[0015] Optionally, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 Independently selected from H atoms, C6–C 30 Aryl, substituted C3–C 30 Aryl, C6–C 30 heteroaryl, substituted C3–C 30 Mixed aromatic compounds.

[0016] Optionally, the C6–C 30 The aryl group is selected from phenyl, naphthyl, biphenyl, naphthylbiphenyl, and phenanthrene; the C3–C 30 The heteroaryl group is selected from thienyl, dibenzothienyl, and triphenylamino.

[0017] Optionally, one or more of the following conditions must be met:

[0018] (i)R 1 R 4 same;

[0019] (ii) R2 and R5 are the same;

[0020] (iii) R3 and R6 are the same;

[0021] (iv)R 7 R 8 same.

[0022] Alternatively, replace C6–C 30 Aryl, substituted C3–C 30 The substituents in heteroaryl groups are selected from alkyl, alkenyl, aldehyde, halogen, haloalkyl, ester-intercalated alkyl, alkoxy, alkylthio, and substituted amino groups.

[0023] Alternatively, replace C6–C 30 Aryl, substituted C3–C 30 The substituents in heteroaryl groups are selected from C1–C 30 Alkyl, C1–C 30 alkenyl, C1–C 30 Aldehyde, halogen, halogenated C1–C 30 C1–C with alkyl or ester insertion 30 Alkyl, C1–C 30 Alkoxy, C1–C 30 Amino groups substituted with alkylthio or phenyl groups.

[0024] Optionally, R 1 R 4 Same or different; R 1 R 4 Independently selected from C6–C substituted with hydrogen, aryl, or alkyl. 30 Aryl, "S-atom-intercalated alkyl" substituted C6–C 30 Aryl, "O-atom inserted alkyl" substituted C6–C 30 Aryl and halogen-substituted C6–C 30 aryl, aryl-substituted C6–C 30 Aryl, halogen-substituted alkyl, C6–C 30 Aryl, "aryl-substituted amino" substituted C6–C 30 Aryl, "ester-intercalated alkyl" substituted C6–C 30 Aryl, C3–C 30 Mixed aromatic compounds.

[0025] Optionally, R 1 R 4 Same or different; R 1 R 4 Independently selected from phenyl, tert-butyl-substituted phenyl, CH3S-substituted phenyl, CH3O-substituted phenyl, naphthyl, phenyl-substituted phenyl, at least one methyl-substituted phenyl, CF3O-substituted phenyl, Br-substituted phenyl, "diphenyl-substituted amino"-substituted phenyl, "ester-intercalated methyl"-substituted phenyl, dibenzothiophene.

[0026] Optionally, R 2 R 5 Same or different; R 2 R 5 Independently selected from C6–C 30 Aryl, "ester-intercalated alkyl" substituted C6–C 30 Aryl and alkyl substituted C6–C 30Aryl, "oxygen-intercalated alkyl" substituted C6–C 30 aryl, aryl-substituted C6–C 30 Aryl, C3–C 30 C6–C substituted with heteroaryl and aldehyde groups 30 Aryl and halogen-substituted C6–C 30 Aryl and alkenyl substituted C6–C 30 Aryl.

[0027] Optionally, R 2 R 5 Same or different; R 2 R 5 Independently selected from phenyl, naphthyl, phenyl substituted with "ester-intercalated methyl", propyl-substituted phenyl, phenanthryl, phenyl substituted with "oxygen-intercalated methyl", biphenyl, thiophene, phenyl substituted with formaldehyde, phenyl substituted with Cl, and phenyl substituted with vinyl.

[0028] Optionally, R 3 R 6 Same or different; R 7 R 8 Same or different; R 3 R 6 R 7 R 8 Independently selected from hydrogen atoms, C6–C 30 Aryl, "ester-intercalated alkyl" substituted C6–C 30 aryl, at least one alkyl-substituted C6–C 30 Aryl.

[0029] Optionally, R 3 R 6 Same or different; R 7 R 8 Same or different; R 3 R 6 R 7 R 8 It is independently selected from hydrogen atoms, phenyl, phenyl substituted with "ester-intercalated methyl", and phenyl substituted with at least one methyl.

[0030] Optionally, the compound has the structure shown in formula (II);

[0031]

[0032] Among them, R 101 R 102 R 103 R 104 R 105 R 106 R107 R 108 R 109 R 110 R 111 R 112 R 113 R 114 R 115 R 116 R 117 R 118 R 119 R 120 R 121 R 122 Independently selected from hydrogen atoms, C1–C 15 Alkyl, substituted C1–C 15 Alkyl, C1–C 15 Alkenyl, substituted C1–C 15 alkenyl, C1–C 15 Alkyne group, substituted C1–C 15 alkynyl group, C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 Heteroaryl, aldehyde, phosphin, halogen, silyl, boron, germanium, arsenic, selenium, and optionally heteroatomic groups selected from the following can be inserted at any position: CO, O, S, SO, SO2, N, NR a -N=, =N-;R 101 R 102 R 103 R 104 R 105 R 106 R 107 R 108 R 109 R 110 R 111 R 112 R 113 R 114 R 115 R 116 R 117 R 118 R 119 R 120 R 121 R 122 Any two structurally adjacent groups can form a ring;

[0033] R a It is independently selected from H, alkyl or aryl.

[0034] Optionally, R 101 R102 R 103 R 104 R 105 R 106 R 107 R 108 R 109 R 110 R 111 R 112 R 113 R 114 R 115 R 116 R 117 R 118 R 119 R 120 R 121 R 122 Independently selected from hydrogen atoms, C1–C 15 Alkyl or halogen-substituted C1–C 15 Alkyl and aryl substituted C1–C 15 Alkyl, S-inserted C1–C 15 Alkyl, O-intercalated C1–C 15 C1–C with alkyl or ester insertion 15 Alkyl, C1–C 15 alkenyl, C6–C 30 Aryl and alkyl substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 The heteroaryl group, or optionally a heteroatom group selected from the following, is inserted at any position: CO, O, S, SO, SO2, N, NR. a -N=, =N-;R 101 R 102 R 103 R 104 R 105 R 106 R 107 R 108 R 109 R 110 R 111 R 112 R 113 R 114 R 115 R 116 R 117 R 118 R 119 R 120 R 121 R 122 Any two structurally adjacent groups can form a ring;

[0035] R a It is independently selected from H, alkyl or aryl.

[0036] Optionally, the compound has the structure shown in formula (III);

[0037]

[0038] Among them, R 201 R 202 R 203 R 204 R 205 R 206 R 207 R 208 R 209 R 210 R 211 R 212 R 213 R 214 R 215 R 216 R 217 R 218 Independently selected from hydrogen atoms, C1–C 15 Alkyl, substituted C1–C 15 Alkyl, C1–C 15 Alkenyl, substituted C1–C 15 alkenyl, C1–C 15 Alkyne group, substituted C1–C 15 alkynyl group, C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 Heteroaryl, aldehyde, phosphin, halogen, silyl, boron, germanium, arsenic, selenium, and optionally heteroatomic groups selected from the following can be inserted at any position: CO, O, S, SO, SO2, N, NR a -N=, =N-;R 201 R 202 R 203 R 204 R 205 R 206 R 207 R 208 R 209 R 210 R 211 R 212 R 213 R 214 R 215 R 216 R 217 R 218Any two structurally adjacent groups can form a ring;

[0039] R a It is independently selected from H, alkyl or aryl.

[0040] Optionally, R 201 R 202 R 203 R 204 R 205 R 206 R 207 R 208 R 209 R 210 R 211 R 212 R 213 R 214 R 215 R 216 R 217 R 218 Independently selected from hydrogen atoms, C1–C 15 Alkyl or halogen-substituted C1–C 15 Alkyl and aryl substituted C1–C 15 Alkyl, S-inserted C1–C 15 Alkyl, O-intercalated C1–C 15 C1–C with alkyl or ester insertion 15 Alkyl, C1–C 15 alkenyl, C6–C 30 Aryl and alkyl substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 The heteroaryl group, or optionally a heteroatom group selected from the following, is inserted at any position: CO, O, S, SO, SO2, N, NR. a -N=, =N-;R 201 R 202 R 203 R 204 R 205 R 206 R 207 R 208 R 209 R 210 R 211 R 212 R 213 R 214 R 215 R 216 R 217 R 218 Any two structurally adjacent groups can form a ring;

[0041] R a It is independently selected from H, alkyl or aryl.

[0042] Optionally, the compound is selected from the following:

[0043]

[0044]

[0045] Another aspect of this application provides a method for preparing the above-mentioned compound, comprising the following steps:

[0046] The reactants containing the compound shown in formula (IV) react in a solvent under the conditions of an oxidizing agent and the action of a base to obtain the compound shown in formula (I);

[0047]

[0048] In equation (IV),

[0049] Wherein, X is selected from nitrogen atom, phosphorus atom, arsenic atom, tellurium atom, and boron atom;

[0050] R' is selected from C1–C 30 Alkyl, substituted C1–C 30 Alkyl, C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 Heteroaryl, amino, substituted amino, and optionally heteroatom groups selected from the following: CO, O, S, SO, SO2, NR are inserted at any position. a -N=, =N-;

[0051] Among them, R 1a R 4a Independently selected from hydrogen, deuterium, C1–C 30 Alkyl, substituted C1–C 30 Alkyl, C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 Heteroaryl, phosphinyl, substituted phosphinyl, boryl, substituted boryl, silyl, substituted silyl, halogen, amino, substituted amino, and optionally heteroatom groups selected from the following: CO, O, S, SO, SO2, NR. a -N=, =N-;

[0052] R a Selected from C6–C 30Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 heteroaryl, C1–C 10 alkenyl, C1–C 10 Substituted alkenyl groups,

[0053] R 3a Hydrogen, deuterium, C1–C 30 Alkyl, substituted C1–C 30 Alkyl, C1–C 30 Alkenyl, substituted C1–C 30 alkenyl, C1–C 30 Alkyne group, substituted C1–C 30 alkynyl group, C6–C 30 Aryl, substituted C6–C 30 Aryl, C3–C 30 heteroaryl, substituted C3–C 30 heteroaryl, C1–C 30 cycloalkyl, substituted C1–C 30 cycloalkyl, C1–C 30 Heterocyclic alkyl, substituted C1–C 30 Heterocyclic alkyl, phosphinyl, halogen, silyl, boronyl, germanium, arsenic, selenium, and optionally heteroatom groups selected from the following: CO, O, S, SO, SO2, NR are inserted at any position. a -N=, =N-;

[0054] R a It is independently selected from H, alkyl or aryl.

[0055] Optionally, the alkaline reagent; preferably, the alkaline reagent is selected from at least one of cesium carbonate, potassium carbonate, sodium carbonate, potassium phosphate, triethylamine, and triethylenediamine.

[0056] Optionally, the molar ratio of the base reagent to the compound shown in formula (IV) is 1:10 to 1:100.

[0057] Optionally, the oxidant is preferably at least one of 2,2,6,6-tetramethylpiperidine nitrogen oxide, oxygen, sodium hypochlorite, aqueous hydrogen peroxide solution, tert-butanol peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, m-chloroperoxybenzoic acid, peracetic acid, and di-tert-butyl peroxide.

[0058] Optionally, the molar ratio of the oxidant to the compound shown in formula (IV) is 1:2 to 1:10.

[0059] Optionally, the organic solvent is selected from at least one of methanol, ethanol, isopropanol, p-xylene, n-butanol, ethyl acetate, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide.

[0060] Optionally, the reaction temperature is 25-150°C, and the reaction time is 0.5-72 hours.

[0061] Another aspect of this application provides the use of the compounds described in any of the above claims, their tautomers, polymorphs, solvates, or salts thereof, in optical super-resolution microscopy, confocal microscopy, wide-field microscopy, fluorescence lifetime imaging microscopy, fluorescence resonance energy transfer microscopy, super-resolution optical wave imaging, fluorescence photoactivated localization microscopy, and light-emitting devices.

[0062] In another aspect of this application, the use of any of the compounds described above, their tautomers, polymorphs, solvates, or salts thereof for cell imaging or fluorescent dyes is provided.

[0063] In this application, "alkyl" refers to a group obtained by losing one H atom from an alkane.

[0064] "Alkenyl" refers to a group formed by the loss of a hydrogen atom from an olefin.

[0065] "Alkyne group" refers to the group formed by losing one hydrogen atom from an alkyne.

[0066] "Cycloalkyl" refers to a group formed by losing one hydrogen atom from a cycloalkane.

[0067] "Heterocyclic alkyl" refers to a group formed by the loss of a hydrogen atom from a heterocyclic alkane.

[0068] "Aryl" refers to the group formed by the loss of one hydrogen atom in an aromatic hydrocarbon.

[0069] "Heteroary aryl" refers to a group obtained by losing one hydrogen atom from a heteroaryl hydrocarbon.

[0070] "Substituted alkyl" and "substituted aryl" refer to alkyl groups substituted by any group and aryl groups substituted by any group, respectively.

[0071] "Heteroatomic groups inserted at any position" means that heteroatomic groups can be inserted into groups by replacing H atoms or C atoms, such as "O atom inserted into methyl group to form CH3O-", "S atom inserted into methyl group to form CH3O-", "NH atom inserted into methyl group to form CH3NH-", "N atom inserted into phenyl group to form pyridyl group", etc.

[0072] "Alkyl-substituted aryl" and "aryl-substituted aryl" respectively represent aryl groups containing alkyl substituents and aryl groups containing aryl substituents, for example... etc.; where "*" represents the connection point of a group.

[0073] In this application, unless otherwise specified, "alkyl", "aryl", etc., may have any number of connection points; generally, there are 1 connection point, 2 connection points, 3 connection points, 4 connection points or 5 connection points.

[0074] “C1–C 30 "The average number of C atoms."

[0075] Halogenated C1–C 30 "Alkyl" refers to alkyl groups with 1-30 carbon atoms that have been halogenated.

[0076] Optionally, "optionally inserted at any position by a heteroatomic group selected from the following: CO, O, S, SO, SO2, NR" a "-N=" and "=N-" indicate that heteroatomic groups can be inserted into any position, such as between any CC, CS, CO, or OO bonds, provided that the valence bond rules are met.

[0077] The structural formulas described in this application are intended to include all isomers (such as enantiomers, diastereomers, and geometric isomers (or conformational isomers)): for example, R-S configurations containing an asymmetric center, (Z) and (E) isomers with double bonds, etc. Therefore, any single stereochemical isomer of the compound of this application, or a mixture of its enantiomers, diastereomers, or geometric isomers (or conformational isomers), is within the scope of this application.

[0078] "Tautomerism" refers to structural isomers with different energies that can cross a low energy barrier and thus interconvert. For example, proton tautomerism (i.e., proton shift) involves interconversion via proton migration. Valence tautomerism involves interconversion via the recombination of some bonding electrons.

[0079] "Solvate" refers to a complex formed by the compound of this invention coordinating with solvent molecules in a specific ratio. The beneficial effects of this application include:

[0080] 1) The compound provided in this application is a novel luminescent core material with a skeleton structure of benzisoindole dimer, which has the advantage of high fluorescence quantum yield, with most compounds having a fluorescence quantum yield greater than 90%.

[0081] 2) The compounds provided in this application have the advantages of good stability, and can be stored at room temperature and remain stable under conditions such as heating and oxidation.

[0082] 3) The compounds provided in this application have emission wavelengths that are generally above 550 nm, and can reach up to 670 nm in the near-infrared region. Furthermore, the chromophores can be further modulated to further enhance the wavelength.

[0083] 4) The compound provided in this application has the advantages of high luminescence sensitivity and a minimum detection concentration of 0.05 micrograms per milliliter. Attached Figure Description

[0084] Figures 1-21 The UV-Vis absorption and emission spectra of compounds FL-1, FL-2, FL-3, FL-4, FL-5, FL-7, FL-8, FL-9, FL-10, FL-11, FL-12, FL-13, FL-14, FL-15, FL-16, FL-17, FL-18, FL-19, FL-20, FL-21, and FL-22 of this application are shown respectively.

[0085] Figure 22 The fluorescence emission spectrum of compound FL-1 in this application is shown in relation to its concentration and luminescence intensity.

[0086] Figure 23 The fluorescence emission spectrum of compound FL-1 at a concentration of 0.05 μg / mL is shown.

[0087] Figures 24-30 The figures are cyclic voltammetry curves for compounds FL-1, FL-7, FL-15, FL-17, FL-18, FL-28, and FL-29 of this application, respectively. Detailed Implementation

[0088] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0089] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.

[0090] The analysis method in the embodiments of this application is as follows:

[0091] NMR analysis was performed using a Bruker AVANCEⅢHD 400 or a NECZ600R.

[0092] UV-Vis absorption and emission spectra were analyzed using a Shimadzu UV-1900 and an Edinburgh FS5-NIR microscope.

[0093] Cyclic voltammetry curves were analyzed using a Shanghai Chenhua electrochemical analyzer.

[0094] Example 1 Preparation of the compound shown in formula (I)

[0095] The preparation method of the compound shown in formula (I) is as follows:

[0096]

[0097] The specific steps are as follows: Compound PA-1 (0.5 mmol) and cesium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then toluene (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-1 (yield 50% based on the mass of product and starting material).

[0098] The reaction conditions and yield calculations in the following examples are the same as in Example 1.

[0099] The NMR data for product detection are as follows:

[0100] 1 H NMR (400MHz, CDCl3) δ9.49 (s, 2H), 8.43 (d, J = 6.9Hz, 4H), 8.36 (s, 2H), 8.12 ( d,J=7.8Hz,2H),7.99(d,J=7.8Hz,2H),7.72–7.65(m,6H),7.61–7.55(m,4H).

[0101]

[0102] The specific steps are as follows: Compound PA-2 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then toluene (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-2 (yield 39% based on the mass of product and starting material).

[0103] The NMR data for product detection are as follows:

[0104] 1 H NMR (600MHz, CDCl3) δ9.51(s,2H),8.40(s,2H),8.38(d,J=8.5Hz,4H),8.13(d,J=7.9H z,2H),7.99(d,J=7.9Hz,2H),7.71(d,J=8.5Hz,4H),7.60–7.54(m,4H),1.46(s,18H). 13C NMR (100MHz, CDCl3) δ169.32,153.53,147.15,136.20,134.44,132.63,132.05,131. 19,128.93,128.75,127.92,126.63,126.27,125.75,124.95,121.83,34.12,30.29.

[0105]

[0106] The specific steps are as follows: Compound PA-3 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-3 (yield 56% based on the mass of product and starting material).

[0107] The NMR data for product detection are as follows:

[0108] 1 H NMR (400MHz, Chloroform-d) δ9.52(s,2H),8.41(m,6H),8.15(d,J=7.6Hz,2H),8.02(d,J=7.4Hz,2H),7.64–7.51(m,8H),2.65(s,6H).

[0109]

[0110] The specific steps are as follows: Compound PA-4 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then, n-butanol (2.5 mL) is added as a solvent. After reacting at 120 degrees Celsius for 1 hour, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-4 (yield 37% based on the mass of product and starting material).

[0111] The NMR data for product detection are as follows:

[0112] 1 H NMR(600MHz,Chloroform-d)δ9.52(s,2H),8.45(d,J=8.7Hz,4H),8.42(s,2H),8.15(d,J= 8.3Hz,2H),8.01(d,J=8.3Hz,2H),7.62–7.54(m,4H),7.21(d,J=8.7Hz,4H),3.98(s,6H).

[0113]

[0114] The specific steps are as follows: Compound PA-7 (0.5 mmol), potassium carbonate (1 mmol), and sodium hypochlorite (1 mmol) are added to a reaction tube. Then, isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and purified by column chromatography to obtain compound FL-7 (yield 32% based on the mass of product and starting material).

[0115] The NMR data for product detection are as follows:

[0116] 1 H NMR(600MHz,Chloroform-d)δ9.39(s,2H),8.07(d,J=8.2Hz,2H),7.85(d,J=7.9Hz,2H),7.70(s,2 H),7.56–7.53(m,2H),7.51–7.48(m,2H),7.43–7.39(m,2H),7.30(d,J=7.7Hz,4H),2.36(s,12H).

[0117]

[0118] The specific steps are as follows: Compound PA-8 (0.5 mmol), potassium carbonate (1 mmol), and hydrogen peroxide (1 mmol) were added to a reaction tube. Then, isopropanol (2.5 mL) was added as a solvent. After reacting at room temperature for 72 hours, the reaction solution was evaporated to dryness and purified by column chromatography to obtain compound FL-8 (yield 38% based on the mass of product and starting material).

[0119] The NMR data for product detection are as follows:

[0120] 1 H NMR(600MHz,THF-d8)δ9.53(s,2H),8.67(d,J=7.9Hz,4H),8.55(s,2H),8.13(d ,J=8.0Hz,2H),8.08(d,J=8.0Hz,2H),7.99(d,J=8.0Hz,4H),7.62–7.57(m,4H).

[0121]

[0122] The specific steps are as follows: Compound PA-14 (0.5 mmol), potassium carbonate (1 mmol), and 2,2,6,6-tetramethylpiperidine nitride were added to a reaction tube. Isopropanol (2.5 mL) was then added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution was evaporated to dryness and purified by column chromatography to obtain compound FL-14 (yield 42% based on the mass of product and starting material).

[0123] The NMR data for product detection are as follows:

[0124] 1 H NMR(600MHz,Chloroform-d)δ9.52(s,2H),8.81(s,2H),8.42–8.39(m,4H),8.32(s ,2H),8.12(d,J=9.6Hz,2H),7.99(d,J=8.7Hz,2H),7.73–7.69(m,6H),4.05(s,6H).

[0125]

[0126] The specific steps are as follows: Compound PA-15 (0.5 mmol) and cesium carbonate (1 mmol) were added to a reaction tube, and oxygen was introduced. Then, toluene (2.5 mL) was added as a solvent. After reacting at room temperature for 72 hours, the reaction solution was evaporated to dryness and purified by column chromatography to obtain compound FL-15 (yield 25% based on the mass of product and starting material).

[0127] The NMR data for product detection are as follows:

[0128] 1 H NMR(600MHz,Chloroform-d)δ9.40(s,2H),8.42(d,J=7.1Hz,4H),8.29(s,2H),7.90–7.84(m,4H),7.69(t,J=7.4Hz,4 H),7.64(t,J=7.2Hz,2H),7.40(d,J=8.0Hz,2H),2.81(t,J=7.6Hz,4H),1.79(q,J=7.6Hz,4H),1.01(t,J=7.3Hz,6H).

[0129]

[0130] The specific steps are as follows: Compound PA-23 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at room temperature for 72 hours, the reaction solution is evaporated to dryness and purified by column chromatography to obtain compound FL-23 (yield 34% based on the mass of product and starting material).

[0131] The NMR data for product detection are as follows:

[0132] 1H NMR(600MHz,Chloroform-d)δ9.31(s,2H),8.36(d,J=6.8Hz,4H),8.10(s,2H),7.88(s,2H),7.83(d,J=8.3 Hz,2H),7.70–7.62(m,8H),6.91(dd,J=17.4,10.9Hz,2H),5.93(d,J=17.5Hz,2H),5.41(d,J=10.7Hz,2H).

[0133]

[0134] The specific steps are as follows: Compound PA-24 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-24 (yield 55% based on the mass of product and starting material).

[0135] The NMR data for product detection are as follows:

[0136] 1 H NMR (400MHz, CDCl3) δ8.17(s,2H),8.02(d,J=8.4Hz,2H),7.92(d,J=7.8Hz,2H),7.80(d d,J=6.3,2.8Hz,4H),7.67(d,J=7.3Hz,4H),7.53–7.40(m,14H),7.27(d,J=7.3Hz,2H). 13 C NMR (101MHz, CDCl3) δ165.72,150.41,140.33,139.27,136.32,134.80,134.43,133.56,1 32.94,131.06,130.20,129.90,129.24,128.34,128.20,127.65,127.45,126.81,122.99.

[0137]

[0138] The specific steps are as follows: Compound PA-25 (0.5 mmol) and potassium carbonate (1 mmol) were added to a reaction tube, and oxygen was introduced. Then, isopropanol (2.5 mL) was added as a solvent. After reacting at room temperature for 72 hours, the reaction solution was evaporated to dryness and passed through a column to obtain compound FL-25 (yield 24% based on the mass of product and starting material).

[0139] The NMR data for product detection are as follows:

[0140] 1 H NMR(600MHz,Chloroform-d)δ8.17(s,2H),8.01(d,J=8.5Hz,2H),7.92(d,J=8.1Hz,2H),7.76(d,J=8.6Hz,4H),7.67–7.6 3(m,4H),7.52–7.48(m,2H),7.47–7.43(m,2H),7.43–7.40(m,4H),7.33(d,J=8.6Hz,4H),7.27–7.25(m,2H),2.57(s,6H).

[0141]

[0142] The specific steps are as follows: Compound PA-26 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-26 (yield 58% based on the mass of product and starting material).

[0143] The NMR data for product detection are as follows:

[0144] 1 H NMR(600MHz,Chloroform-d)δ8.18(s,2H),8.02(d,J=8.6Hz,2H),7.93(d,J=8.0Hz,2H),7.81(d,J=8.9Hz,4H),7.67 (dd,J=8.2,1.2Hz,4H),7.51–7.47(m,2H),7.46–7.40(m,6H),7.28–7.24(m,2H),7.00(d,J=8.9Hz,4H),3.91(s,6H).

[0145]

[0146] The specific steps are as follows: Compound PA-27 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at room temperature for 48 hours, the reaction solution is evaporated to dryness and purified by column chromatography to obtain compound FL-27 (yield 32% based on the mass of product and starting material).

[0147] The NMR data for product detection are as follows:

[0148] 1H NMR(600MHz,Chloroform-d)δ8.16(s,2H),8.01(s,2H),7.86(d,J=8.7Hz,2H),7.78(d,J=8.8Hz,4H),7.64(d,J=7.1Hz,4H),7.45(t,J=7.9Hz,6H),7 .27(t,J=8.2Hz,2H),6.99(d,J=8.8Hz,4H),4.06(t,J=6.6Hz,4H),1.87–1 .82(m,4H),1.52–1.48(m,4H),1.42–1.29(m,24H),0.89(t,J=6.9Hz,6H).

[0149]

[0150] The specific steps are as follows: Compound PA-28 (0.5 mmol) and potassium carbonate (1 mmol) were added to a reaction tube, and oxygen was introduced. Then, isopropanol (2.5 mL) was added as a solvent. After reacting at room temperature for 36 hours, the reaction solution was evaporated to dryness and passed through a column to obtain compound FL-28 (yield 51% based on the mass of product and starting material).

[0151] The NMR data for product detection are as follows:

[0152] 1 H NMR(600MHz,Chloroform-d)δ8.25(s,2H),8.04(d,J=8.6Hz,2H),7.96(d,J=9.3Hz,2H),7.91(d,J=8.5Hz,4H),7.73(d,J=8. 5Hz,4H),7.72–7.69(m,8H),7.53–7.50(m,4H),7.49–7.47(m,2H),7.47–7.44(m,6H),7.42–7.39(m,2H),7.30–7.27(m,2H).

[0153]

[0154] The specific steps are as follows: Compound PA-29 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-29 (yield 75% based on the mass of product and starting material).

[0155] The NMR data for product detection are as follows:

[0156] 1H NMR(600MHz,Chloroform-d)δ8.39(s,2H),8.32(s,2H),8.07(ddd,J=11.8,6.9,1.4Hz,4H),8.00–7.92 (m,8H),7.78–7.75(m,4H),7.61–7.57(m,4H),7.55–7.53(m,2H),7.51–7.47(m,6H),7.30–7.27(m,2H).

[0157]

[0158] The specific steps are as follows: Compound PA-30 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-30 (yield 35% based on the mass of product and starting material).

[0159] The NMR data for product detection are as follows:

[0160] 1 H NMR(600MHz,Chloroform-d)δ8.17(s,2H),8.01(d,J=8.0Hz,4H),7.94(d,J=8.0Hz,2H),7.8 8(d,J=8.5Hz,2H),7.69–7.62(m,8H),7.57–7.48(m,8H),7.46(t,J=7.5Hz,2H),3.87(s,6H).

[0161]

[0162] The specific steps are as follows: Compound PA-31 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-31 (yield 33% based on the mass of product and starting material).

[0163] The NMR data for product detection are as follows:

[0164] 1 H NMR(400MHz,Chloroform-d)δ8.19–8.11(m,4H),7.93(d,J=7.3Hz,2H),7.85( d,J=6.3Hz,4H),7.55–7.44(m,10H),7.33(s,4H),6.95(s,2H),2.36(s,12H).

[0165]

[0166] The specific steps are as follows: Compound PA-32 (0.5 mmol) and potassium carbonate (1 mmol) are added to a reaction tube, and oxygen is introduced. Then isopropanol (2.5 mL) is added as a solvent. After reacting at 80 degrees Celsius for 72 hours, the reaction solution is evaporated to dryness and passed through a column to obtain compound FL-32 (yield 52% based on the mass of product and starting material).

[0167] The NMR data for product detection are as follows:

[0168] 1 H NMR (400MHz, Chloroform-d) δ8.13(s,2H),8.00(d,J=8.4Hz,2H),7.93(d,J=7.9Hz,2H),7.72–7.58(m,12H),7.56–7.39(m,8H),7.28–7.24(m,2H). 13 C NMR (100MHz, CDCl3) δ164.70,150.43,140.25,139.47,135.88,134.52,133.53,133.20,1 32.97,131.49,130.99,130.67,129.92,128.36,127.71,127.04,126.88,124.79,122.86.

[0169] Characterization of the compound shown in formula (I) in Example 2

[0170] Table 1 - Structures, numbers, and physicochemical data of preferred compounds

[0171]

[0172]

[0173]

[0174]

[0175] Example 2: Fluorescence performance test of the compound shown in formula (I)

[0176] The fluorescence properties of the compound shown in formula (I) were tested using the following method: 1 mg of sample was accurately weighed and dissolved in 10 mL of tetrahydrofuran. First, the absorption spectrum of the compound was tested, and then the emission spectrum was measured at the wavelength of maximum absorption. The maximum emission wavelength was obtained from the emission spectrum, and this wavelength was selected as the optimal excitation wavelength for the compound. The compound was then excited at the optimal excitation wavelength to obtain the final emission spectrum.

[0177] Typical test results are as follows Figures 1-21 The images shown are the UV-Vis absorption and emission spectra of compounds FL-1, FL-2, FL-3, FL-4, FL-5, FL-7, FL-8, FL-9, FL-10, FL-11, FL-12, FL-13, FL-14, FL-15, FL-16, FL-17, FL-18, FL-19, FL-20, FL-21, and FL-22 of this application, respectively.

[0178] Figure 22 The fluorescence emission spectrum of compound FL-1 in this application is shown in relation to its concentration and luminescence intensity.

[0179] Figure 23 The fluorescence emission spectrum of compound FL-1 at a concentration of 0.05 μg / mL is shown.

[0180] Figures 1-23 This indicates that these compounds have potential applications in fluorescent materials and fluorescent probes.

[0181] Example 3: Electrical performance testing of the compound shown in formula (I)

[0182] The electrical properties of the compound shown in formula (I) were tested using the following method: tetrabutylammonium hexafluorophosphate was used as the electrolyte at a concentration of 0.1 M, and tetrahydrofuran was used as the solvent at a concentration of 5 mL. A glassy carbon electrode was used as the working electrode, a platinum wire electrode as the auxiliary electrode, a saturated calomel electrode as the reference electrode, and the scan rate was 100 mV / s.

[0183] Typical test results are as follows Figures 24-30 The figures shown are cyclic voltammetry curves for compounds FL-1, FL-7, FL-15, FL-17, FL-18, FL-28, and FL-29 of this application, respectively.

[0184] Figures 24-30 This indicates that these compounds have two reduced states and may be used as conductive organic compounds or photo-redox catalysts.

[0185] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A compound, characterized in that, It has the structure shown in equation (II); (II) Among them, R 101 R 102 R 103 R 104 R 105 R 106 R 107 R 108 R 109 R 110 R 111 R 112 R 113 R 114 R 115 R 116 R 117 R 118 R 119 R 120 R 121 R 122 Independently selected from hydrogen atoms, C1–C 15 Alkyl, S-inserted C1–C 15 Alkyl, O-intercalated C1–C 15 Alkyl, C1–C 15 alkenyl, C6–C 30 Aryl.

2. A compound, characterized in that, The compound is selected from the following: 。 3. The method for preparing the compound according to claim 1, characterized in that, Includes the following steps: The reactants containing the compound shown in formula (IV) react in a solvent under the conditions of an oxidizing agent and the action of a base to obtain the compound shown in formula (II); In equation (IV), Where X is a nitrogen atom; R' is a phenyl group; Among them, R 1a Corresponding to formula (II) in claim 1 and ; R 2a Corresponding to formula (II) in claim 1 and ; R 3a Corresponding to formula (II) in claim 1 and ; R 4a For H; The alkali is selected from at least one of cesium carbonate, potassium carbonate, sodium carbonate, potassium phosphate, triethylamine, and triethylenediamine; The oxidant is selected from at least one of 2,2,6,6-tetramethylpiperidine nitrogen oxides, oxygen, sodium hypochlorite, aqueous hydrogen peroxide solution, tert-butanol peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, m-chloroperoxybenzoic acid, peracetic acid, and di-tert-butyl peroxide.

4. The preparation method according to claim 3, characterized in that, The molar ratio of the alkaline reagent to the compound shown in formula (IV) is 1:10 to 1:

100.

5. The preparation method according to claim 3, characterized in that, The molar ratio of the oxidant to the compound shown in formula (IV) is 1:2 to 1:

10.

6. The preparation method according to claim 3, characterized in that, The solvent is selected from at least one of methanol, ethanol, isopropanol, p-xylene, n-butanol, ethyl acetate, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide.

7. The preparation method according to claim 3, characterized in that, The reaction temperature is 25-150℃, and the reaction time is 0.5-72 hours.

8. The use of the compound of claim 1 or 2 as a reagent for preparing optical super-resolution microscopy, confocal microscopy, wide field-of-view microscopy, fluorescence lifetime imaging microscopy, fluorescence resonance energy transfer microscopy, super-resolution optical wave imaging, and fluorescence photoactivated localization microscopy.

Images