Multi-site substituted bromopyrene intermediate, derivative thereof, preparation method and application

Abstract

The invention belongs to the field of synthesis of fine chemical intermediates, and discloses a multi-site substituted bromopyrene intermediate and a derivative, a preparation method and application thereof. The molecular structural formula of the bromopyrene intermediate is # imgabs0 #, wherein X1, X2 and X3 are bromine atoms or H; and X1, X2 and X3 are not H at the same time. R1 is an alkane having 1 to 90 carbon atoms, a heterocyclic alkane having 1 to 90 carbon atoms, a substituted aromatic hydrocarbon having 5 to 90 carbon atoms, an aryloxy group having 5 to 90 carbon atoms, an aromatic amine having 5 to 90 carbon atoms, a boron aromatic hydrocarbon having 5 to 90 carbon atoms, or an aromatic heterocyclic group having 5 to 90 carbon atoms. The prepared pyrenyl luminescent material can effectively improve the solubility of target molecules, and is applied to the fields of organic luminescent devices, organic photovoltaic devices, perovskite solar devices, fluorescent falsification prevention, thermal response stimuli response, biological imaging and the like.

Description

Technical Field

[0001] The present invention belongs to the cross-field of fine chemicals, optoelectronic materials and biomedicine, and specifically relates to a class of multi-site substituted bromopyrene intermediates and derivatives thereof, a preparation method and application thereof. Background Art

[0002] In recent years, polycyclic aromatic hydrocarbons, such as naphthalene, anthracene, perylene, pyrene, etc., have attracted great attention in organic synthesis, materials science and industry due to their high thermal stability, chemical stability, excellent ordered structure and unique optoelectronic properties. Among them, pyrene is a tetraphenyl fused-ring aromatic compound. Its rigid planar structure makes it exhibit strong deep blue light emission, high quantum yield and high carrier mobility in solution. It is widely used in organic light-emitting devices, organic photovoltaic devices, perovskite solar devices, etc. In addition, due to the strong π-π stacking effect in the aggregated state, they exhibit weak fluorescence and low quantum yield. However, compounds with spatially distorted conformations, such as tetraphenylethylene (TPE), cyanostyrene and its derivatives, exhibit opposite optical behaviors. In the past few decades, due to the intrinsic fluorescence properties of pyrene, molecular aggregation can only be suppressed by functionalizing the pyrene core or constructing pyrene-based aggregation-induced emission. Therefore, it is of great significance to develop pyrene-based intermediates to synthesize new functional materials.

[0003] Pyrene has 10 reaction sites, including 4 active reaction sites (1-, 3-, 6- and 8-positions), K-regions (4-, 5-, 9- and 10-positions) and nodal points (2- and 7-positions). Among them, the reaction activities of 1-, 3-, 6- and 8-positions are relatively high and the differences are not large, while the reaction activities of K-regions and nodal points are relatively poor. At present, the types of pyrene-based intermediates developed at the nodal points of pyrene are limited, and the complex synthesis methods require a lot of time and manpower. The lengthy and complicated synthesis and purification routes reduce the overall yield, greatly increase the cost, and hinder its practical application. It is urgent to develop a method for synthesizing pyrene-based intermediates that is simple, efficient, green, environmentally friendly, and economical. Introducing oxygen atoms into pyrene-based organic molecules can effectively regulate their luminescence properties and carrier transport properties. Through further molecular modification, pyrene-based organic functional luminescent materials have been greatly enriched, promoting their practical applications in organic light-emitting devices, organic photovoltaic devices, perovskite solar devices, fluorescent anti-counterfeiting, thermal response stimulus response and biological imaging. Summary of the invention

[0004] The primary purpose of the present invention is to provide a class of multi-site substituted bromopyrene intermediates.

[0005] Another object of the present invention is to provide a method for synthesizing the above-mentioned multi-site substituted bromopyrene intermediate, which uses 2,7-dihydroxypyrene as a raw material to prepare the bromopyrene intermediate through substitution and bromination reactions; the process design is reasonable, the yield is high, the reaction conditions are mild, and the raw material price is low.

[0006] Another object of the invention is to prepare a pyrene-based organic functional luminescent material based on a multi-site substituted bromopyrene intermediate. The pyrene-based organic functional luminescent material is prepared by performing multi-site functional substitution at the 1-, 1,6- or 1,8-site of pyrene through a palladium-catalyzed coupling reaction.

[0007] A further object of the invention is to provide an application of the above-mentioned pyrene-based organic functional luminescent material.

[0008] The purpose of the present invention is achieved through the following technical solutions:

[0009] The molecular structure of a multi-site substituted bromopyrene intermediate is shown in formula (1):

[0010]

[0011] Wherein, X1, X2, and X3 are bromine atoms or H, and X1, X2, and X3 are not H at the same time; R1 is an alkane having 1 to 90 carbon atoms, a heterocycloalkane having 1 to 90 carbon atoms, a substituted aromatic hydrocarbon having 5 to 90 carbon atoms, an aryloxy group having 5 to 90 carbon atoms, an aromatic amine having 5 to 90 carbon atoms, a boroarene having 5 to 90 carbon atoms, or an aromatic heterocyclic group having 5 to 90 carbon atoms.

[0012] Preferably, its molecular structure is as shown in 1-3:

[0013]

[0014] The method for preparing the multi-site substituted bromopyrene intermediate comprises the following steps:

[0015] Under a protective atmosphere, 2,7-bis(R1)-pyrene is added with a brominating agent and an organic solvent, and the mixture is stirred at room temperature for 2 to 24 hours to carry out a bromination reaction to obtain a multi-site substituted bromopyrene intermediate.

[0016] Preferably, the protective atmosphere is nitrogen or argon; the brominating agent is one or more of N-bromosuccinimide, benzyltrimethylammonium tribromide, hydrobromic acid solution or bromine water; the organic solvent is one or more of tetrahydrofuran, dichloromethane, chloroform, N,N-dimethylformamide; the molar ratio of the 2,7-bis(R1)-pyrene to the brominating agent is 1:(1.2-2.5).

[0017] Under a protective atmosphere, 2,7-dihydroxypyrene is added to a halogenated compound, a base and an organic solvent, and heated and stirred at 80 to 120° C. for 12 to 24 hours to carry out a substitution reaction to obtain 2,7-bis(R1)pyrene.

[0018] Preferably, the protective atmosphere is nitrogen or argon; the halogenated compound is one or more of halogenated alkanes, halogenated aromatic hydrocarbons, halogenated aromatic oxides, halogenated aromatic amines, halogenated boroaromatic hydrocarbons, and halogenated aromatic heterocyclic groups; the base is one or more of cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, and sodium tert-butoxide; the organic solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, acetonitrile, 1,4-dioxane, and methyl isoflurane; the molar ratio of 2-7-dihydroxypyrene: halogenated compound: base and organic solvent is 1:(2-4):(5-20):(50-500).

[0019] The structure of a type of multi-site substituted pyrene-based luminescent material is shown in formula (2):

[0020]

[0021] Wherein, R1 and R2 are both alkanes having 1 to 90 carbon atoms, heterocycloalkanes having 1 to 90 carbon atoms, substituted aromatic hydrocarbons having 5 to 90 carbon atoms, aryloxy groups having 5 to 90 carbon atoms, aromatic amines having 5 to 90 carbon atoms, boron aromatic hydrocarbons containing 5 to 90 carbon atoms, or aromatic heterocyclic groups having 5 to 90 carbon atoms; R3 and R4 are H, alkanes having 1 to 90 carbon atoms, heterocycloalkanes having 1 to 90 carbon atoms, substituted aromatic hydrocarbons having 5 to 90 carbon atoms, aryloxy groups having 5 to 90 carbon atoms, aromatic amines having 5 to 90 carbon atoms, boron aromatic hydrocarbons containing 5 to 90 carbon atoms, or aromatic heterocyclic groups having 5 to 90 carbon atoms, and R3 and R4 are not H at the same time.

[0022] Preferably, R1, R2, and R3 are not H at the same time, and the molecular structure of the multi-site substituted pyrene-based luminescent material is as follows:

[0023] As shown in formula 4-6:

[0024]

[0025] The preparation method of the multi-site substituted pyrene-based luminescent material is as follows: under the protection of a protective atmosphere, the multi-site substituted bromopyrene intermediate is added with a palladium catalyst, aromatic boric acid and its derivatives, an inorganic base and a solvent, and a palladium-catalyzed coupling reaction is performed at 50 to 100° C. to perform functional substitution at multiple sites of pyrene to prepare the material.

[0026] Preferably, the protective atmosphere is nitrogen or argon; the palladium catalyst is one or more of tetrakis(triphenylphosphine)palladium, palladium acetate, tri(tert-butylphosphine) tetrafluoroborate or tri(dibenzylideneacetone)dipalladium, dichlorobis(triphenylphosphine)palladium; the inorganic base is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium hydroxide; the solvent is one or more of toluene, ethanol, water, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, and triethylamine; the molar ratio of the multi-site substituted bromopyrene intermediate: aromatic boronic acid and its derivatives: palladium catalyst: inorganic base: solvent is 1:(1-5):(0.01-0.2):(5-20):(50-500).

[0027] The above-mentioned multi-site substituted pyrene-based luminescent materials are used in the fields of organic light-emitting devices, organic photovoltaic devices, perovskite solar devices, fluorescent probes, fluorescent anti-counterfeiting, thermal response stimulus response and biological imaging.

[0028] The present invention introduces different substituent groups at the 2 and 7-positions of pyrene, functionalizes pyrene at the nodal nodes, and selectively performs bromination reaction and palladium-catalyzed coupling reaction at the 1-, 3-, 6- and 8-positions, thereby regulating the molecular structure and steric hindrance, resulting in different optical and physical properties, which is beneficial to the preparation of pyrene-based functional materials with different properties, promotes the development of pyrene-based functional materials, and is beneficial to the application of such luminescent molecules in the fields of organic light-emitting devices, organic photovoltaic devices, perovskite solar devices, fluorescent anti-counterfeiting, thermal response stimulus response and biological imaging.

[0029] The synthetic route of the multi-site substituted bromopyrene intermediate of the present invention is as follows:

[0030]

[0031] Wherein, R1 and R2 are both alkanes having 1 to 90 carbon atoms, heterocycloalkanes having 1 to 90 carbon atoms, substituted aromatic hydrocarbons having 5 to 90 carbon atoms, aryloxy groups having 5 to 90 carbon atoms, aromatic amines having 5 to 90 carbon atoms, boroarene groups having 5 to 90 carbon atoms or aromatic heterocyclic groups having 5 to 90 carbon atoms.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. The present invention uses 2,7-dihydroxypyrene as a raw material to prepare a bromopyrene intermediate through substitution and bromination reactions; the number of modification sites of the obtained intermediate is large and controllable, filling the gap of this type of pyrene-based intermediates, and the pyrene-based derivatives prepared by molecular modification can be used as pyrene-based organic light-emitting materials.

[0034] 2. The pyrene-based luminescent material of the present invention uses a multi-site substituted bromopyrene intermediate as a precursor, and introduces an R1 substituent group at the 2,7-position of pyrene, so that the 1,3,6,8-position substituent groups can form a larger dihedral angle with the pyrene ring, effectively inhibiting the interaction between molecules, improving the luminescence efficiency and carrier mobility of the target molecule, and adjusting the charge within the molecule by controlling different substitution sites, thereby improving its charge transfer performance. In addition, the introduction of the R1 substituent group at the 2,7-position of pyrene can improve the solubility of the molecule, making it easier to purify the product;

[0035] 3. The synthesis method of the present invention has the advantages of simple experimental operation, mild reaction conditions, high intermediate yield, etc.;

[0036] 4. The pyrene-based organic light-emitting material of the present invention can effectively improve the solid-state light-emitting efficiency of the material and is applied to the fields of organic light-emitting devices, organic photovoltaic devices, perovskite solar devices, fluorescent anti-counterfeiting, thermal response stimulus response and biological imaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is the molecular structural formula of the multi-site substituted pyrene-based luminescent material of the present invention.

[0038] Figure 2 2,7-dihexyloxypyrene of Example 1 1 HNMR spectrum.

[0039] Figure 3 2,7-dihexyloxypyrene of Example 1 13 C NMR spectrum.

[0040] Figure 4 This is the HRMS chart of 2,7-dihexyloxypyrene of Example 1.

[0041] Figure 5 1-bromo-2,7-bis(n-hexyloxy)pyrene of Example 2 1 H NMR spectra.

[0042] Figure 6 This is the HRMS chart of 1-bromo-2,7-bis(n-hexyloxy)pyrene of Example 2.

[0043] Figure 7 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene of Example 3 1 HNMR spectrum.

[0044] Figure 8 This is the HRMS chart of 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene of Example 3.

[0045] Fig. 91,8-dibromo-2,7-bis(n-hexyloxy)pyrene of Example 3 1 HNMR spectrum.

[0046] Fig.10 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene of Example 3 13 C NMR spectrum.

[0047] Fig.11 This is the HRMS chart of 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene of Example 3.

[0048] Fig.12 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 4 1 HNMR spectrum.

[0049] Fig.13 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 4 13 C NMR spectrum.

[0050] Fig.14 This is the HRMS chart of 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 4.

[0051] Fig.15 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 5 1 HNMR spectrum.

[0052] Fig.16 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 5 13 CNMR image.

[0053] Fig.17 This is the HRMS chart of 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 5.

[0054] Fig.18 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 6 1 HNMR spectrum.

[0055] Fig.19 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 6 13 CNMR image.

[0056] Fig. 20This is the HRMS chart of 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene of Example 6. DETAILED DESCRIPTION

[0057] The content of the present invention is further described below in conjunction with specific examples, but it should not be construed as limiting the present invention. If not specifically indicated, the technical means used in the examples are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0058] Example 1 Preparation of 2,7-dihexyloxypyrene

[0059] Under nitrogen protection, 2,7-dihydroxy-pyrene (Py-2OH) (1 eq.), iodohexane (2 eq.) and cesium carbonate (5 eq.) were added to a double-necked flask, dissolved in N,N-dimethylformamide (10 mL), heated to reflux at 120° C. for 24 h, cooled to room temperature after the reaction, extracted with dichloromethane three times, washed with saturated brine, and separated by chromatographic column after reduced pressure rotary evaporation. The eluent was a mixed solution of dichloromethane and n-hexane. After separation and purification, the target product 2,7-bishexyloxypyrene was obtained with a yield of about 70%. Its synthesis route is shown in formula (1).

[0060]

[0061] Figure 1 The molecular structure of the multi-site substituted pyrene-based luminescent material of the present invention is prepared using a multi-site substituted bromopyrene intermediate as a raw material. Figure 2 2,7-dihexyloxypyrene obtained in this example 1 H NMR spectrum, Figure 3 The 2,7-dihexyloxypyrene obtained in this example 13 C NMR spectrum. Figure 4 HRMS diagram of 2,7-dihexyloxypyrene obtained in this example. Figure 2-4 It can be seen that 2,7-dihexyloxypyrene was successfully prepared.

[0062] Example 2 Preparation of 1-bromo-2,7-bis(n-hexyloxy)pyrene

[0063] Under nitrogen protection, 2,7-bishexyloxypyrene (1 eq.) and N-bromosuccinimide (1 eq.) prepared in Example 1 were added to a dry double-necked bottle, and tetrahydrofuran (9 mL) was added to dissolve. After stirring at room temperature overnight, a large amount of anhydrous ethanol was added to quench the reaction mixture and stirred for 10 min. Then a certain amount of precipitate appeared and was filtered under reduced pressure. The residue was dissolved in CHCl3-hexane (V CHCl3 :V己烷 =1:2) mixed solvent to obtain 1-bromo-2,7-bis(n-hexyloxy)pyrene with a yield of about 80%. The synthesis route is shown in formula (2).

[0064]

[0065] Figure 5 1-Bromo-2,7-bis(n-hexyloxy)pyrene obtained in this example 1 HNMR diagram, Figure 6 HRMS diagram of 1-bromo-2,7-bis(n-hexyloxy)pyrene obtained in this example. Figure 5-6 It can be seen that 1-bromo-2,7-bis(n-hexyloxy)pyrene was successfully prepared.

[0066] Example 3 Preparation of 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene and 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene

[0067] Under nitrogen protection, 2,7-bis(n-hexyloxy)pyrene (1 eq.) and N-bromosuccinimide (2 eq.) prepared in Example 1 were added to a dry double-necked flask, and tetrahydrofuran (15 mL) was added to dissolve. After stirring at room temperature overnight, a large amount of anhydrous ethanol was added to quench the reaction mixture and stirred for 10 min. Then a certain amount of precipitate appeared and was filtered under reduced pressure to obtain a mixture of 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene and 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene. According to the difference in solubility between the two, the mixture was recrystallized in CHCl3 to first obtain 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene (yield of about 68%), and then 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene (yield of about 29%) was obtained. According to the results of nuclear magnetic resonance, the quantitative ratio of the two was close to 2:1. The synthesis route is shown in formula (3).

[0068]

[0069] Figure 7 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene obtained in this example 1 HNMR diagram, Figure 8 HRMS diagram of 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene obtained in this example. Figure 7-8 It can be seen that 1,6-dibromo-2,7-bis(n-hexyloxy)pyrene was successfully prepared. Fig. 9 The 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene obtained in this example 1 H NMR spectrum, Fig.10 The 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene obtained in this example 13 C NMR spectrum, Fig.11 HRMS diagram of 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene obtained in this example. Figure 9-11 It can be seen that 1,8-dibromo-2,7-bis(n-hexyloxy)pyrene was successfully prepared.

[0070] Example 4 Preparation of 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene

[0071] Under nitrogen protection, 1-bromo-2,7-bis(hexyloxy)pyrene (1 eq.), 4-triphenylamine borate (1 eq.) and potassium carbonate (5 eq.) prepared in Example 2 were added to a dry double-necked flask, dissolved in a mixed solution (8 mL) of toluene, ethanol and water in a volume ratio of 2:1:1, heated to reflux at 90°C for 24 h, cooled to room temperature after the reaction, extracted with dichloromethane three times, washed with saturated brine, and separated by chromatographic column after rotary evaporation. The eluent was a mixed solution of dichloromethane and n-hexane to obtain the target product 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene with a yield of about 87%. Its synthesis route is shown in formula (4).

[0072]

[0073] Fig.12 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example 1 H NMR spectrum, Fig.13 The 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example 13 C NMR spectrum, Fig.14 HRMS diagram of 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example. Figure 12-14 It can be seen that 1-(4-triphenylamine)-2,7-bis(hexyloxy)pyrene was successfully prepared.

[0074] Example 5 Preparation of 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene

[0075] Under nitrogen protection, 1,6-dibromo-2,7-bis(hexyloxy)pyrene (1 eq.) and 4,4'-dimethoxy-4"-boric acid triphenylamine (2 eq.), potassium carbonate (10 eq.), and tetrakis(triphenylphosphine)palladium (0.05 eq.) prepared in Example 3 were added into a dry double-necked flask, dissolved in a mixed solution (8 mL) of toluene, ethanol, and water in a volume ratio of 2:1:1, heated to reflux at 90°C for 24 h, cooled to room temperature after the reaction, extracted with dichloromethane three times, washed with saturated brine, and separated by chromatographic column after rotary evaporation. The eluent was a mixed solution of dichloromethane and n-hexane to obtain the target product 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene with a yield of about 44%. Its synthesis route is shown in Formula (5).

[0076]

[0077] Fig.15 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example 1 HNMR diagram, Fig.16 The 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example 13 C NMR spectrum, Fig.17 HRMS diagram of 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example. Figure 15-17 It can be seen that 1,6-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene was successfully prepared.

[0078] Example 6 Preparation of 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene

[0079] Under nitrogen protection, 1,8-dibromo-2,7-bis(hexyloxy)pyrene (1 eq.) and 4,4'-dimethoxy-4"-boric acid triphenylamine (2 eq.), potassium carbonate (10 eq.), and tetrakis(triphenylphosphine)palladium (0.05 eq.) prepared in Example 3 were added into a dry double-necked flask, dissolved in a mixed solution (8 mL) of toluene, ethanol, and water in a volume ratio of 2:1:1, heated to reflux at 90°C for 24 h, cooled to room temperature after the reaction, extracted with dichloromethane three times, washed with saturated brine, and separated by chromatographic column after rotary evaporation. The eluent was a mixed solution of dichloromethane and n-hexane to obtain the target product 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene with a yield of about 81%. Its synthesis route is shown in formula (6).

[0080]

[0081] Fig.18 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example 1 HNMR diagram, Fig.19 The 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example 13 C NMR spectrum, Fig. 20 HRMS diagram of 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene obtained in this example. Figure 18-20 It can be seen that 1,8-bis(4,4'-dimethoxy-4"triphenylamine)-2,7-bis(hexyloxy)pyrene was successfully prepared.

[0082] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A multi-site substituted bromopyrene intermediate, characterized in that: The molecular structure of the multi-site substituted bromopyrene intermediate is shown in formula (1): Wherein, X1, X2, and X3 are bromine atoms or H; and X1, X2, and X3 are not H at the same time; R1 is an alkane having 1 to 90 carbon atoms, a heterocycloalkane having 1 to 90 carbon atoms, a substituted aromatic hydrocarbon having 5 to 90 carbon atoms, an aryloxy group having 5 to 90 carbon atoms, an aromatic amine having 5 to 90 carbon atoms, a boroarene having 5 to 90 carbon atoms, or an aromatic heterocyclic group having 5 to 90 carbon atoms.

2. The multi-site substituted bromopyrene intermediate according to claim 1, characterized in that: The bromopyrene intermediate is 1-bromo-2,7-bis-R1-group pyrene, 1,6-dibromo-2,7-bis-R1-group pyrene or 1,8-dibromo-2,7-bis-R1-group pyrene, and its structural formula is as follows:

3. The method for preparing a multi-site substituted bromopyrene intermediate according to claim 1 or 2, characterized in that: The multi-site substituted bromopyrene intermediate is prepared by adding 2,7-bis(R1)-group pyrene to a brominating agent and an organic solvent under a protective atmosphere, and stirring at 20 to 40° C. for 12 to 36 hours to carry out a bromination reaction.

4. The method for preparing a multi-site substituted bromopyrene intermediate according to claim 3, characterized in that: The 2,7-bis(R1)-group pyrene is prepared by adding 2-7-dihydroxypyrene to a halogenated compound, a base and an organic solvent under a protective atmosphere, and heating and stirring at 80 to 120° C. for 12 to 24 hours to carry out a substitution reaction.

5. The method for preparing a multi-site substituted bromopyrene intermediate according to claim 4, characterized in that: The protective atmosphere is nitrogen or argon; the halogenated compound is one or more of halogenated alkanes, halogenated aromatic hydrocarbons, halogenated aromaticoxy groups, halogenated aromatic amines, and halogenated aromatic heterocyclic groups; the base is one or more of cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, or sodium tert-butoxide; the organic solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, acetonitrile, 1,4-dioxane, and methyl isoflurane; the molar ratio of 2-7-dihydroxypyrene: halogenated compound: base and organic solvent is 1:(2-4):(5-20):(50-500).

6. The method for preparing a multi-site substituted bromopyrene intermediate according to claim 5, characterized in that: The halogenated alkyl is methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl iodide, hexyl iodide, heptane iodide, octane iodide or 1-bromotodecane; the halogenated aromatic hydrocarbon is bromobenzene, p-bromotoluene, 1-bromo-4-tert-butyl or 4-(trifluoromethyl)benzyl bromide; the halogenated aromaticoxy is 4-bromoanisole or 4-bromo-4',4'-dimethoxytriphenylamine; the halogenated aromatic amine is 4-bromoaniline, 4-bromo-o-phenylenediamine or 4-bromotriphenylamine; the halogenated aromatic heterocyclic group is 2-bromothiophene, 2-bromothiazole or 3-bromo-10H-phenothiazine.

7. The method for preparing a multi-site substituted bromopyrene intermediate according to claim 3, characterized in that: The protective atmosphere is nitrogen or argon; the brominating agent is one or more of N-bromosuccinimide, benzyltrimethylammonium tribromide, hydrobromic acid or bromine water; the organic solvent is one or more of tetrahydrofuran, dichloromethane, chloroform or N,N-dimethylformamide; the molar ratio of the 2,7-bis(R1)-pyrene to the brominating agent is 1:(1.2-2.5).

8. A multi-site substituted pyrene-based luminescent material, characterized in that: The multi-site substituted pyrene-based functional luminescent material is prepared by adding the bromopyrene intermediate described in claim 1 or 2 to a palladium catalyst, aromatic boric acid and its derivatives, an inorganic base and an organic solvent under a protective atmosphere, and performing a palladium-catalyzed coupling reaction at 50 to 100° C. to perform functional substitution at different sites of pyrene; The molecular structure of the multi-site substituted pyrene functional luminescent material is shown in formula (2): Wherein, R1 and R2 are both alkanes having 1 to 90 carbon atoms, heterocycloalkanes having 1 to 90 carbon atoms, substituted aromatic hydrocarbons having 5 to 90 carbon atoms, aryloxy groups having 5 to 90 carbon atoms, aromatic amines having 5 to 90 carbon atoms, boron aromatic hydrocarbons containing 5 to 90 carbon atoms, or aromatic heterocyclic groups having 5 to 90 carbon atoms; R3 and R4 are H, alkanes having 1 to 90 carbon atoms, heterocycloalkanes having 1 to 90 carbon atoms, substituted aromatic hydrocarbons having 5 to 90 carbon atoms, aryloxy groups having 5 to 90 carbon atoms, aromatic amines having 5 to 90 carbon atoms, boron aromatic hydrocarbons containing 5 to 90 carbon atoms, or aromatic heterocyclic groups having 5 to 90 carbon atoms, and R3 and R4 are not H at the same time.

9. The multi-site substituted pyrene-based luminescent material according to claim 8, characterized in that: The protective atmosphere is nitrogen or argon; the palladium catalyst is one or more of tetrakis(triphenylphosphine)palladium, palladium acetate, tri(tert-butylphosphine)tetrafluoroborate or tri(dibenzylideneacetone)dipalladium or dichlorobis(triphenylphosphine)palladium; the inorganic base is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate or sodium hydroxide; the organic solvent is one or more of toluene, ethanol, water, tetrahydrofuran, acetonitrile, N,N-dimethylformamide or triethylamine; the molar ratio of the bromopyrene intermediate: aromatic boric acid and its derivatives: palladium catalyst: inorganic base is 1:(1.5-10):(0.1-0.3):(5-40).

10. Use of the multi-site substituted pyrene-based luminescent material according to claim 8 or 9 in the fields of organic light-emitting devices, organic photovoltaic devices, perovskite solar devices, fluorescent anti-counterfeiting, thermal response stimulus response or biological imaging.

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