Preparation method of supramolecular assembly fluorescent dye and pyrenyl pyridine derivative used in preparation method

Abstract

The invention belongs to the field of fluorescent materials, and relates to a novel pyrenyl pyridine derivative supramolecular assembly fluorescent material. The invention particularly relates to a preparation method and a characterization method of a pyrenyl pyridine derivative and supramolecular assembly fluorescent material. The invention provides a pyrenyl pyridine derivative and a preparation method thereof. The invention also provides a preparation method of the supramolecular assembly fluorescent dye, and the supramolecular assembly fluorescent dye is obtained by using the pyrenyl pyridine derivative, taking cucurbituril as a host unit and taking the pyrenyl pyridine derivative as a guest unit through host-guest interaction.

Description

Technical Field

[0001] This invention belongs to the field of fluorescent materials and relates to a novel supramolecular assembly fluorescent material of pyrene-pyridine derivatives. Specifically, it relates to a method for preparing and characterizing a pyrene-pyridine derivative and a supramolecular assembly fluorescent material. Background Technology

[0002] Fluorescence is the luminescence phenomenon produced when molecules absorb energy, electrons transition to a singlet excited state, and then radiatively transition back to the ground state. With changing needs, the development direction of fluorescent materials has continuously adjusted. From initially meeting the needs of white light illumination, to the application of halogen powders to obtain a more natural light sensation, and now to the sophisticated molecular or crystal-designed multifunctional synergistic integrated fluorescent materials, their applications have expanded to multiple fields such as plant cultivation, military lighting, health monitoring, and biosensing, showing broad application prospects.

[0003] In recent years, the much-discussed organic conjugated systems have been widely applied in fields such as organic optoelectronics, fluorescence sensing, and bioimaging.

[0004] Patent CN120441492A discloses a molecular system with blue fluorescence, using phenanthreneimidazole as the donor unit and a fused-ring aromatic conjugated group as the acceptor unit, which shows great potential for applications in organic light-emitting diodes (OLEDs). The application of novel organic conjugated systems focuses on the design and synthesis of novel functional molecules. Pyrene, a member of the polycyclic aromatic hydrocarbon family, exhibits both electron-donating and electron-withdrawing properties, resulting in excellent optical properties. Pyrene possesses the following advantages: 1) it has good thermal stability; 2) it has high luminous efficiency. Furthermore, the pyrene unit has a large conjugated system range, significant electron delocalization, and readily undergoes π-π* transitions upon photoexcitation. Based on these advantages, pyrene is commonly used as a fluorescent unit for constructing large conjugated systems.

[0005] Patent CN120097867A provides a mechanically color-changing pyrene derivative material, which has important applications in fingerprint extraction. However, its raw materials are not easy to obtain, the cost is relatively high, and it is not water-soluble.

[0006] Patent CN119954685A discloses a water-soluble monobenzene ring fluorescent dye with a simple structure, but it is difficult to modify. Therefore, the preparation of novel high-performance organic optoelectronic materials containing pyrene fused ring structural units and the exploration of their luminescence mechanisms are of great significance. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a method for preparing supramolecular assembly fluorescent dyes and the pyrene pyridine derivatives used therein.

[0008] To address the above problems, this invention provides a pyrene-pyridine derivative with the following structural formula: .

[0009] This invention also provides a method for preparing the above-mentioned pyrene pyridine derivative, comprising the following steps: 1-Bromo-6-(4-pyridyl)pyrene and 1-(3-bromopropyl)-4-(4-bromophenyl)pyridine-1-onium were added to... N,N The reaction is carried out in dimethylformamide under heating at a temperature of 60-120°C for 24-120 hours (preferably 60-90°C for 48±2 hours). The molar ratio of 1-bromo-6-(4-pyridyl)pyrene to 1-(3-bromopropyl)-4-(4-bromophenyl)pyridine-1-onium is 1:1 to 2 (preferably 1:1.1 to 1.3, more preferably 1:1.15 to 1.2). After filtration, pyrene-pyridine derivatives were obtained.

[0010] Generally speaking: 1 mmol of 1-bromo-6-(4-pyridyl)pyrene is prepared with (10 ± 2) mL. NN -Dimethylformamide.

[0011] The chemical formula for the reaction is as follows:

[0012] As an improvement to the preparation method of the pyrene pyridine derivative of the present invention, the preparation method of 1-bromo-6-(4-pyridyl)pyrene is as follows: 1,6-Dibromopyrene, pyridine-4-boronic acid, and palladium catalyst were added to tetrahydrofuran, followed by the addition of an alkaline solution. The reaction was carried out under an inert gas atmosphere (including N2). The reaction temperature was 60-100℃, and the reaction time was 24-120 h (preferably 60-80℃, 60±2 h). The molar ratio of 1,6-dibromopyrene to pyridine-4-boronic acid was 1:2-5.2, and the molar ratio of 1,6-dibromopyrene to palladium catalyst was 1:0.1-0.5. The volume ratio of tetrahydrofuran to alkaline solution is 2~4:1; the alkaline solution is an aqueous solution with a concentration of 1~3 mol / L of alkali or alkaline salt. The reaction product was cooled (to room temperature), filtered, and the filtrate was separated by column chromatography using dichloromethane / methanol as the eluent to give 1-bromo-6-(4-pyridyl)pyrene.

[0013] Generally speaking: use (120±20) mL of tetrahydrofuran for every 7 mmol of 1,6-dibromopyrene.

[0014] The chemical formula for the reaction is as follows: .

[0015] As a further improvement to the preparation method of the pyrene pyridine derivative of the present invention: The palladium catalyst is tetra(triphenylphosphine)palladium, or a mixture of tri(dibenzylacetone)dipalladium and triphenylphosphine in a molar ratio of 1:4.

[0016] As a further improvement to the preparation method of the pyrene pyridine derivative of the present invention: The base in the alkaline solution is NaOH or KOH, and the alkaline salt in the alkaline solution is K2CO3.

[0017] As a further improvement to the preparation method of the pyrene pyridine derivative of the present invention: The eluent is a mixture of dichloromethane and methanol in a volume ratio of 200 to 500:1.

[0018] This invention also provides a method for preparing supramolecular assembly fluorescent dyes, using the above-mentioned pyrene pyridine derivatives, with cucurbita as the host unit and pyrene pyridine derivatives as guest units, to obtain supramolecular assembly fluorescent dyes (the guest units are embedded in the cavities of the ring structure of the host unit) through host-guest interactions.

[0019] An improvement to the preparation method of the supramolecular assembly fluorescent dye of the present invention: Cucurbitaurea is cucurbita[7]urea, and the molar ratio of pyrene pyridine derivative to cucurbita[7]urea is 1:0.1~2; the resulting supramolecular assembly fluorescent dye is named Py / CB[7] assembly fluorescent dye; Cucurbitaurea is cucurbita[8]urea, and the molar ratio of pyrene pyridine derivative to cucurbita[8]urea is 1:0.1~1; the resulting supramolecular assembly fluorescent dye is named Py / CB[8] assembly fluorescent dye.

[0020] An improvement to the preparation method of the supramolecular assembly fluorescent dye of the present invention: A system was formed by dissolving pyrene pyridine derivatives and cucurbituril in deionized water and then sonicating for 4-6 minutes (at 30±5℃) to obtain a solution of supramolecular assembled fluorescent dye.

[0021] As a further improvement to the preparation method of the supramolecular assembly fluorescent dye of the present invention: In the system, the concentration of the pyrene pyridine derivative is 1 × 10⁻⁶. -4 ~1×10 -5 M.

[0022] Currently known pyrene-based fluorescent materials are generally not water-soluble and their synthesis methods are quite challenging. Therefore, it is crucial to obtain a novel fluorescent material that is water-soluble, emits fluorescence at both short-wavelength blue and long-wavelength orange light, can self-assemble, and has a simple synthesis method, which would help expand the practical applications of such materials.

[0023] The target object structure of the present invention is highly modifiable, amphiphilic, and easy to self-assemble.

[0024] In this invention: Pyrene pyridine derivatives were dissolved in deionized water to prepare solutions, and their UV-Vis absorption spectra were measured in the 220-600 nm range, while their fluorescence spectra were measured in the 230-800 nm range. Acetonitrile was used as the organic solvent to prepare acetonitrile / water solutions of pyrene pyridine derivatives with different acetonitrile ratios, and their fluorescence spectra were then measured.

[0025] The assembly mode of the pyrene-pyridine derivative supramolecular assembly was analyzed by measuring the ultraviolet-visible absorption spectrum of the aqueous solution.

[0026] The fluorescence spectrum and quantum yield of the pyrene pyridine derivative supramolecular assembly aqueous solution were detected by fluorescence spectroscopy to detect the fluorescence properties and quantum yield of the supramolecular assembly fluorescent material.

[0027] Dynamic light scattering was used to measure the particle size of the pyrene-pyridine derivative supramolecular assembly in aqueous solution to analyze the size of the aggregates.

[0028] The morphology of the aggregates was observed by field emission scanning electron microscopy of the aqueous solution of the pyrene pyridine derivative supramolecular assembly.

[0029] Compared with the prior art, the present invention has the following technical advantages: (1) The pyrene pyridine derivative of the present invention is a novel fluorescent material with high structural conjugation (containing pyrene group itself) and strong modifiability. Due to the use of organic pyridine onium salt, it has amphiphilicity, high thermal stability, and the required raw materials are easy to obtain.

[0030] (2) The pyrene pyridine derivatives described in this invention are easy to self-assemble and exhibit multi-color light properties after self-assembly. Attached Figure Description

[0031] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0032] Figure 1 The structural formula of a pyrene-pyridine derivative; Figure 2 The 1H NMR spectrum of 1-bromo-6-(4-pyridyl)pyrene obtained in step 1 of Example 1; Figure 3 The carbon NMR spectrum of 1-bromo-6-(4-pyridyl)pyrene obtained in step 1 of Example 1; Figure 4The mass spectrum of 1-bromo-6-(4-pyridyl)pyrene obtained in step 1 of Example 1; Figure 5 The 1H NMR spectrum of the pyrene pyridine derivative obtained in step 2 of Example 1; Figure 6 The carbon NMR spectrum of the pyrene pyridine derivative obtained in step 2 of Example 1; Figure 7 The mass spectrum of the pyrene pyridine derivative obtained in step 2 of Example 1 is shown below. Figure 8 The image shows the UV-Vis absorption spectrum of the pyrene pyridine derivative aqueous solution obtained in step 3 of Example 1. Figure 9 The fluorescence spectrum of the pyrene pyridine derivative aqueous solution obtained in step 3 of Example 1 is shown below. Figure 10 The images show pyrene pyridine derivative acetonitrile / water solutions with different acetonitrile ratios (volume ratio of acetonitrile to water) obtained in step 3 of Example 1 under 365 nm UV light irradiation; the acetonitrile volume ratios of the samples from left to right are 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90% respectively. Figure 11 The fluorescence spectra of pyrene pyridine derivatives in acetonitrile / aqueous solutions with different acetonitrile ratios obtained in step 3 of Example 1 are shown. Figure 12 The UV-Vis absorption spectrum of the Py / CB[7] assembly fluorescent dye prepared by using pyrene pyridine derivative and cucurbit[7]urea in step 4 of Example 1 is obtained by titrating an aqueous solution of the dye. Figure 13 The UV-Vis absorption spectrum of the Py / CB[8] assembly fluorescent dye prepared by using pyrene pyridine derivative and cucurbit[8]urea in step 5 of Example 1 is obtained by titrating an aqueous solution of the dye. Figure 14 The fluorescence spectrum of the Py / CB[7] assembly fluorescent dye in step 6 of Example 1; Figure 15 The fluorescence spectrum of the Py / CB[8] assembly fluorescent dye in step 6 of Example 1; Figure 16 This is a field emission scanning electron microscope image of the fluorescent dye in the Py / CB[7] assembly in step 7 of Example 1; Figure 17 The dynamic light scattering particle size distribution of the Py / CB[8] assembly fluorescent dye in step 7 of Example 1 is shown in the image. Figure 18 The image is a field emission scanning electron microscope image of the fluorescent dye of the Py / CB[8] assembly in step 7 of Example 1. Detailed Implementation

[0033] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0034] 1-Bromo-6-(4-pyridyl)pyrene (CAS: 1622011-21-5) can be prepared by the method described in Example 1 below.

[0035] Example 1: Preparation of pyrene pyridine derivatives and supramolecular assembly fluorescent materials, performed sequentially using the following steps: Step 1: Add 7 mmol of 1,6-dibromopyrene, 36 mmol of pyridine-4-boronic acid and 0.7 mmol of tetra(triphenylphosphine)palladium to 120 mL of tetrahydrofuran to form a reaction system. Prepare 40 mL of potassium carbonate solution with a molar concentration of 2 mol / L using deionized water and slowly add it to the reaction system using a syringe (addition time is about 5 minutes). Heat to 80 °C and stir for 60 h under an inert gas atmosphere.

[0036] The obtained reactants were post-treated as follows: after cooling to room temperature, the mixture was filtered to remove the filter residue. The filtrate was subjected to column chromatography (300-400 mesh silica gel column) using dichloromethane / methanol = 400:1 (v / v) as the eluent. The elution flow rate was 0.03 column volumes / minute (approximately 15 mL / min), and the amount of eluent used was 15 column volumes. All eluent was collected and dried (at 35 °C for 24 h) to obtain 1.92 g of 1-bromo-6-(4-pyridyl)pyrene (yellow solid), with a yield of 77.0%.

[0037] 1-Bromo-6-(4-pyridyl)pyrene, i.e., 1-bromo-6-(4-pyridyl)pyrene, has the following structural formula:

[0038] The proton NMR spectrum of 1-bromo-6-(4-pyridyl)pyrene is shown below. Figure 2 The carbon NMR spectrum is as follows: Figure 3 Mass spectrum as shown Figure 4 .

[0039] Step 2: Add 1 mmol of 1-bromo-6-(4-pyridyl)pyrene and 1.2 mmol of 1-(3-bromopropyl)-4-(4-bromophenyl)pyridin-1-onium (CAS: 3044127-72-9) to 10 mL N,N The mixture was reacted in dimethylformamide at 90°C for 48 hours, filtered, and the filtrate was removed to obtain 0.59 g of pyrene pyridine derivative (yellow solid), with a yield of 74.3%.

[0040] The structural formulas of pyrene pyridine derivatives are as follows:

[0041] The proton NMR spectrum of pyrene pyridine derivatives is shown below. Figure 5 The carbon NMR spectrum is as follows: Figure 6 Mass spectrum as shown Figure 7 .

[0042] Step 3: Take 5 × 10⁵ units of the pyrene pyridine derivative obtained in Step 2. -5 mmol was dissolved in 5 mL of deionized water to obtain a pyrene-pyridine derivative solution; 2.5 × 10⁻⁶ cucurbita[7]urea -3 mmol was dissolved in 5 mL of deionized water to obtain cucurbit[7]urea solution; According to the molar ratio of cucurbita[7]urea:pyrene pyridine derivative = 0~2.0:1 (specifically as follows) Figure 12 The corresponding cucurbita[7]urea solution was added to the pyrene pyridine derivative solution, and the mixture was sonicated (30°C, 5 minutes) to obtain an aqueous solution of the Py / CB[7] assembly fluorescent material. The titration process can be monitored using a UV-Vis spectrophotometer.

[0043] Figure 12 The 0eq~2.0eq values ​​represent the molar ratio of cucurbita[7]urea to pyrene pyridine derivatives, respectively. Figure 12 It can be seen that when 0-1.2eq of CB[7] is added, the characteristic absorption peak at 421nm is blue shifted to 401nm and the absorption intensity gradually increases. When 1.2eq-2eq is added, the absorption peak wavelength remains unchanged, but the intensity is weakened. The intensity of the characteristic absorption peak at 309nm continues to decrease.

[0044] When the molar ratio of cucurbit[7]urea:pyrene pyridine derivative is 2.0:1, the resulting assembly of fluorescent dye is Py / CB[7]=1:2.

[0045] Step 4: Take 5 × 10 of the pyrene pyridine derivative obtained in Step 2. -5 mmol was dissolved in 5 mL of deionized water to obtain a pyrene-pyridine derivative solution; Cucurbita[8]urea 5×10 -4 mmol was dissolved in 5 mL of deionized water to obtain cucurbit[8]urea solution; According to the molar ratio of cucurbita[8]urea:pyrene pyridine derivative = 0~1.0:1 (specifically as follows) Figure 13 The corresponding cucurbita[8]urea solution was added to the pyrene pyridine derivative solution, and the mixture was sonicated (30°C, 5 minutes) to obtain an aqueous solution of the Py / CB[8] assembly fluorescent material. The titration process can be monitored using a UV-Vis spectrophotometer.

[0046] Figure 13 The 0eq~1.0eq values ​​represent the molar ratio of cucurbita[8]urea to the pyrene pyridine derivative, respectively. Figure 13 It can be seen that after adding 0eq~1.0eq CB[8], the intensity of the characteristic absorption peak at 309nm decreased and redshifted, eventually redshifting to 323nm. The absorption peak at 438nm disappeared and a new absorption peak appeared at 470nm.

[0047] When the molar ratio of cucurbit[8]urea:pyrene pyridine derivative is 1.0:1, the resulting assembly of fluorescent dye is Py / CB[8]=1:1.

[0048] Experiment 1: Investigating the effect of organic solvents on pyrene pyridine derivatives (to demonstrate that pyrene pyridine derivatives have the property of being pleochroically tunable): The pyrene pyridine derivative obtained in step 2 of Example 1 was dissolved in deionized water to prepare a 1×10⁻⁶ solution. -5 Solutions with concentration M were tested for UV-Vis absorption spectra in the 220-600 nm range and fluorescence spectra in the 230-800 nm range. Acetonitrile was used as the organic solvent to prepare 1×10⁻⁶ acetonitrile / water pyrene pyridine derivatives with different acetonitrile-to-water volume ratios. -5 The fluorescence spectrum of a solution with concentration M was tested.

[0049] Taking "10%CH3CN" as an example, it represents a volume ratio of acetonitrile to deionized water of 1:9. In this case, the concentration of the pyrene pyridine derivative in the resulting "acetonitrile / water pyrene pyridine derivative solution" is 1×10⁻⁶. -5 M.

[0050] according to Figures 8-11 It can be observed that under light excitation at a wavelength of 310 nm, without the addition of acetonitrile, the pyrene pyridine derivative molecule exhibits a weak emission peak at 380 nm and a strong emission peak at 592 nm, which are identified as characteristic emissions of the 4-(bromophenyl)pyridine ononium moiety and the pyrene moiety, respectively. The total concentration of the pyrene pyridine derivative was fixed at 1 × 10⁻⁶. -5 M, when the proportion of acetonitrile is increased, the fluorescence emission intensity is enhanced. At a 90% acetonitrile ratio, the fluorescence emission intensity increases to 3.8 times the original value, and at a 90% acetonitrile ratio, the fluorescence emission intensity increases to 8.9 times that in pure aqueous solution. Figure 11 These are luminescence images of pyrene pyridine derivatives in acetonitrile / water mixed solvents with different proportions from 0% to 90% under 365nm ultraviolet light, with the acetonitrile content increasing from 0% to 90% from left to right. The luminescence of the solution changes from orange to yellow, and the fluorescence emission intensity is significantly enhanced, which is consistent with the result of a blue shift in the maximum fluorescence emission wavelength in the emission spectrum.

[0051] Experiment 2: The Py / CB[7]=1:2 assembled fluorescent dye obtained in step 3 of Example 1 and the Py / CB[8]=1:1 assembled fluorescent dye obtained in step 4 of Example 1 were subjected to fluorescence spectroscopy using a fluorescence spectrometer (according to JY / T0571-2020). The results are as follows. Figure 14 , Figure 15 As stated above.

[0052] All light emitted from the sample was captured using an integrating sphere. The quantum yield was calculated directly by software by comparing the fluorescence spectra of the blank and the sample. The concentration of the pyrene pyridine derivative was 1.0 × 10⁻⁶. -5 M. Among them, the fluorescence quantum yield of the Py / CB[7] = 1:2 assembled fluorescent dye is 13.48%, and the fluorescence quantum yield of the Py / CB[8] = 1:1 assembled fluorescent dye is 8.02%.

[0053] The fluorescence quantum yield is equal to the ratio of the number of fluorescent photons emitted by a substance to the number of excitation photons absorbed by it, i.e., .

[0054] Experiment 3: The Py / CB[7]=1:2 assembly fluorescent dye obtained in step 3 of Example 1 was subjected to field emission scanning electron microscopy (according to JY / T 0584-2020). The results are as follows: Figure 16 As can be seen from the figure, the diameter of the microspheres is around 190 nm.

[0055] The Py / CB[8]=1:1 assembled fluorescent dye obtained in step 4 of Example 1 was subjected to dynamic light scattering particle size test (according to GB / T 29022-2021) and field emission scanning electron microscopy (according to JY / T 0584-2020). The results are as described above. Figure 17 As stated in 18, according to Figure 17 It can be determined that the particle size is mainly distributed around 894 nm. According to... Figure 18 It can be determined that the diameter of the microsphere is approximately 186 nm.

[0056] Experiment 4, the Py / CB[7]=1:2 assembled fluorescent dye obtained in step 3 of Example 1, and the Py / CB[8]=1:1 assembled fluorescent dye obtained in step 4 of Example 1, can be used with reference to the existing CN120774890A patent. Adding 0.1-2% mass fraction of assembled fluorescent dye to the system can achieve the dyeing effect.

[0057] Example 2: Preparation method of pyrene pyridine derivatives: Step 1: Add 7 mmol of 1,6-dibromopyrene, 36 mmol of pyridine-4-boronic acid, 0.7 mmol of tris(dibenzylacetone)dipalladium and 2.8 mmol of triphenylphosphine to 120 mL of tetrahydrofuran to form a reaction system. Prepare 40 mL of potassium carbonate solution with a molar concentration of 2 mol / L using deionized water and slowly add it to the reaction system using a syringe. Heat to 80 °C and stir for 60 h under an inert gas atmosphere.

[0058] The subsequent processing was the same as step 1) of Example 1, yielding 1.33 g of 1-bromo-6-(4-pyridyl)pyrene (yellow solid), with a yield of 54.5%.

[0059] Step 2 is the same as step 2 in Example 1.

[0060] Example 3: Preparation method of pyrene pyridine derivatives: Step 1: In Example 1, step 1) is modified from "stirring at 80°C for 60 h" to "stirring at 60°C for 60 h". The rest is the same as step 1 in Example 1. 1.27 g of 1-bromo-6-(4-pyridyl)pyrene (yellow solid) was obtained, with a yield of 50.8%.

[0061] Step 2 is the same as step 2 in Example 1.

[0062] Example 4: Preparation method of pyrene pyridine derivatives: Step 1: In Example 1, step 1) is changed from "stirring at 80°C for 60 h" to "stirring at 100°C for 60 h". The rest is the same as in Step 1 of Example 1. 0.69 g of 1-bromo-6-(4-pyridyl)pyrene (yellow solid) was obtained, with a yield of 27.6%.

[0063] Step 2 is the same as step 2 in Example 1.

[0064] Example 5: Preparation method of pyrene pyridine derivatives: Step 1 is the same as step 1 in Example 1.

[0065] Step 2: Change "react at 90℃ for 48h" to "react at 60℃ for 48h", the rest is the same as step 2 of Example 1; 0.11g of yellow solid was obtained, yield 13.6%.

[0066] Example 6: Preparation method of pyrene pyridine derivatives: Step 1 is the same as step 1 in Example 1.

[0067] Step 2: Change "react at 90°C for 48 hours" to "react at 120°C for 48 hours", the rest is the same as step 2 of Example 1; 0.36 g of yellow solid was obtained, with a yield of 45.2%.

[0068] Example 7: Preparation method of pyrene pyridine derivatives: Step 1: Replace "36 mmol pyridine-4-boronic acid" in Step 1) of Example 1 with "14 mmol pyridine-4-boronic acid", and the rest is the same as Step 1 of Example 1. 1.38 g of 1-bromo-6-(4-pyridyl)pyrene (yellow solid) was obtained, with a yield of 55.2%.

[0069] Step 2 is the same as step 2 in Example 1.

[0070] Comparative Example 1, compared to Example 1, the following changes were made: Cancel step 1 1-bromo-6-(4-pyridyl)pyrene was replaced with the existing compound 1-(1H-imidazolyl)pyrene, and the amount remained unchanged at 1 mmol; the rest was the same as in Example 1.

[0071] The structure of 1-(1H-imidazolyl)pyrene is as follows:

[0072] Therefore, the derivative obtained in step 2 was named Py2, with a yield of 61.2%.

[0073] The structure of Py2 is as follows:

[0074] The supramolecular fluorescent material obtained by derivative Py2 and cucurbit[7]urea is named Py2 / CB[7] assembly fluorescent dye (Py2 / CB[7]=1:2), and the supramolecular fluorescent material obtained by derivative Py2 and cucurbit[8]urea is named Py2 / CB[8] assembly fluorescent dye (Py2 / CB[8]=1:1); its performance parameters are: the fluorescence quantum yield of Py2 / CB[7] assembly fluorescent dye is 10.75%, and the fluorescence quantum yield of Py2 / CB[8] assembly fluorescent dye is 5.62%.

[0075] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A pyrene pyridine derivative, characterized in that... The structural formula is: 。 2. A method for preparing pyrene pyridine derivatives, characterized in that... Includes the following steps: 1-Bromo-6-(4-pyridyl)pyrene and 1-(3-bromopropyl)-4-(4-bromophenyl)pyridin-1-onium were added to... N,N The reaction is carried out in dimethylformamide under heating at a temperature of 60-120°C for 24-120 hours. The molar ratio of 1-bromo-6-(4-pyridyl)pyrene to 1-(3-bromopropyl)-4-(4-bromophenyl)pyridine-1-onium is 1:1~2; After filtration, pyrene-pyridine derivatives were obtained.

3. The method for preparing the pyrene pyridine derivative according to claim 2, characterized in that... The preparation method of 1-bromo-6-(4-pyridyl)pyrene is as follows: 1,6-Dibromopyrene, pyridine-4-boronic acid, and palladium catalyst were added to tetrahydrofuran, followed by the addition of an alkaline solution. The reaction was carried out under an inert gas atmosphere at a temperature of 60–100 °C for 24–120 h. The molar ratio of 1,6-dibromopyrene to pyridine-4-boronic acid was 1:2–5.2, and the molar ratio of 1,6-dibromopyrene to palladium catalyst was 1:0.1–0.

5. The volume ratio of tetrahydrofuran to alkaline solution is 2~4:1; the alkaline solution is an aqueous solution with a concentration of 1~3 mol / L of alkali or alkaline salt. The reaction product was cooled and filtered. The filtrate was separated by column chromatography using dichloromethane / methanol as the eluent to obtain 1-bromo-6-(4-pyridyl)pyrene.

4. The method for preparing the pyrene pyridine derivative according to claim 3, characterized in that: The palladium catalyst is tetra(triphenylphosphine)palladium, or a mixture of tri(dibenzylacetone)dipalladium and triphenylphosphine in a molar ratio of 1:

4.

5. The method for preparing the pyrene pyridine derivative according to claim 4, characterized in that: The base in the alkaline solution is NaOH or KOH, and the alkaline salt in the alkaline solution is K2CO3.

6. The method for preparing the pyrene pyridine derivative according to claim 5, characterized in that: The eluent is a mixture of dichloromethane and methanol in a volume ratio of 200 to 500:

1.

7. A method for preparing supramolecular assembly fluorescent dyes, characterized in that: Using the pyrene pyridine derivative as described in claim 1, Using cucurbituril as the host unit and pyrene pyridine derivatives as guest units, supramolecular assembled fluorescent dyes are obtained through host-guest interactions.

8. The method for preparing supramolecular assembly fluorescent dye according to claim 7, characterized in that: Cucurbitaurea is cucurbita[7]urea, and the molar ratio of pyrene pyridine derivative to cucurbita[7]urea is 1:0.1~2; the resulting supramolecular assembly fluorescent dye is named Py / CB[7] assembly fluorescent dye; Cucurbitaurea is cucurbita[8]urea, and the molar ratio of pyrene pyridine derivative to cucurbita[8]urea is 1:0.1~1; the resulting supramolecular assembly fluorescent dye is named Py / CB[8] assembly fluorescent dye.

9. The method for preparing supramolecular assembly fluorescent dye according to claim 8, characterized in that: A system was formed by dissolving pyrene pyridine derivatives and cucurbituril in deionized water and then sonicating for 4-6 minutes to obtain supramolecular assembled fluorescent dyes.

10. The method for preparing supramolecular assembly fluorescent dye according to claim 9, characterized in that: In the system, the concentration of the pyrene pyridine derivative is 1 × 10⁻⁶. -4 ~1×10 -5 M.

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