CN115594629A - Carbazole derivative with AEE characteristic and preparation method and application thereof - Google Patents
Carbazole derivative with AEE characteristic and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title abstract 3
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 31
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention belongs to the technical field of aggregation-induced enhanced luminescent materials, and discloses carbazole derivatives with AEE characteristics, and a preparation method and application thereof. Two compounds were successfully prepared by experimental methods of Suzuki coupling and purified by column chromatography. The carbazole derivative prepared by the preparation method has excellent AEE effect, and the luminous intensity can be respectively improved by 8.3 times and 5 times. When two compounds with AEE effect are in solid state, the absolute quantum yield respectively reaches 26.79% and 23.03%, which shows that the compounds have good luminous effect and both have development prospect as OLED materials, and the compound TPC-CH 3 Can be used for specific detection of TNP.
Description
Technical Field
The invention belongs to the technical field of aggregation-induced enhanced luminescent materials, and relates to carbazole derivatives with AEE characteristics, and a preparation method and application thereof.
Background
Most organic light-emitting molecules can emit strong fluorescence in a dilute solution, but the fluorescence disappears in a concentrated solution, and the quenching (ACQ) effect caused by the aggregation often limits the application of the light-emitting molecules in the field of materials. In 2001, the Tang Benzhong topic group discovered a molecule with properties that are distinct from the traditional aggregation induced quenching (ACQ), and the Aggregation Induced Emission (AIE) concept was first proposed. In 2002, the Aggregation Enhanced Emission (AEE) materials reported by Park et al are slightly different from the AIE effect materials, and AEE-property compounds can emit fluorescence even in a dispersed state. AEE materials have received much attention for their application in various fields such as chemical sensors, bio-imaging, green energy devices, and fingerprint sensing.
Organic electroluminescent diodes have become the mainstream display technology in the electronic field, have the characteristics of an OLED display such as strong luminous capacity, good transparency and good flexibility, and have more excellent performance compared with a Liquid Crystal Display (LCD); in addition to displays, OLEDs are also powerful candidates for lighting. As a lighting source, the OLED has the same excellent performances of green, environmental protection, energy conservation and the like as an inorganic LED, and also has the unique advantages different from the inorganic LED. The OLED is the only area light source at present, and the light utilization rate of the OLED is greatly improved; the OLED can be made on ultrathin, light-weight, flexible and bendable substrates such as plastic and the like, has the characteristics of lightness, thinness, flexibility and the like, and is more flexible and convenient to apply; OLEDs are currently the only illumination source that can be made transparent. However, the strong pi-pi accumulation of the ACQ molecules causes the development of the ACQ molecules in the aspect of OLED to be greatly limited, and many materials cannot be applied to the photoelectric field.
2,4,6-Trinitrophenol (TNP) as a strong nitro explosive is the main component of industrial explosives, and its explosive power is 22 times stronger than that of the well-known 2,4,6-trinitrotoluene. It is also used as a pigment in the dye and leather industries, and also causes environmental problems such as pollution and skinning corrosion in industrial production. After TNP is inhaled, eaten or absorbed through skin carelessly, the skin is easy to yellow and stain, contact dermatitis, conjunctivitis and bronchitis are caused, headache, dizziness, nausea and vomiting, anorexia, diarrhea, fever and other symptoms can be caused, and peripheral neuritis, bladder irritation symptoms and liver and kidney damage can be caused sometimes. Under the current large environment that explosion attack is high and public safety and life safety are highly valued, the rapid, efficient and high-sensitivity TNP detection is an urgent challenge in the aspects of homeland safety and environmental protection. In recent decades, there have been many methods for detecting TNP, including gas chromatography-electron capture detection, gas chromatography-mass spectrometry, X-ray imaging, etc., but these methods all require bulky and expensive equipment, complicated operation and time-consuming procedures, and are not convenient for on-site detection.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the carbazole derivative with AEE characteristics and the preparation method and application thereof, and the carbazole derivative obtained by the preparation method has excellent AEE effect, and the luminous intensity can be respectively improved by 8.3 times and 5 times.
The above purpose of the invention is realized by the following technical scheme:
a carbazole derivative with AEE characteristics has a structural formula shown in a formula I:
wherein R is selected from-NH 2 and-CH 3.
The preparation method of the carbazole derivative with AEE characteristics has the following synthetic route
The preparation method specifically comprises the following steps:
will be provided with
(0.5g, 1.52-1.53 mmol), 4- (9H-carbazol-9-yl) phenylboronic acid (1.31-1.32g, 4.55-4.59 mmol), anhydrous potassium carbonate (1.75g, 12.7 mmol), pd (PPh) 3 ) 4 (0.1g, 0.087mmol) was placed in a two-necked flask and 125mL of 1, 4-dioxane or 125mL of DMSO and 25mL of distilled water were added thereto, stirred and heated to 90-100 ℃ under nitrogen atmosphere and reacted for 24 hours. After the reaction is finished, cooling to room temperature, extracting with distilled water and dichloromethane, drying with anhydrous sodium sulfate, filtering, and spinning out the solvent. Purifying by column chromatography with petroleum ether/ethyl acetate as eluent, and recrystallizing with ethanol to obtain crystal or powder.
The invention also aims to protect the application of the carbazole derivative with the AEE characteristic prepared by the preparation method as a fluorescent probe for identifying small molecular substances, in particular to the application of the carbazole derivative with the AEE characteristic as a fluorescent probe for identifying 2,4,6-Trinitrophenol (TNP).
The carbazole derivative TPC-CH prepared by the invention 3 、TPC-NH 2 Has aggregation-induced enhanced emission (AEE) characteristics, and has potential as novel OLED, wherein the compound TPC-CH 3 Can be used for detecting TNP (the detection limit is 0.305. Mu.M).
Compared with the prior art, the invention has the beneficial effects that:
the carbazole derivative prepared by the preparation method has excellent AEE effect, and the luminous intensity can be respectively improved by 8.3 times and 5 times. Two compounds were successfully prepared by experimental methods of Suzuki coupling and purified by column chromatography. When two compounds with AEE effect are in solid state, the absolute quantum yield respectively reaches 26.79% and 23.03%, which shows that the compounds have good luminous effect and both have development prospect as OLED materials, and the compound TPC-CH 3 Can be used for specifically detecting TNP (the detection limit is 0.305 mu M).
Drawings
FIG. 1 is a photograph of a compound prepared in example 1 of the present invention 1 H NMR spectrum.
FIG. 2 shows the compound prepared in example 1 of the present invention in THF/C 2 H 5 Fluorescence spectra and trend plots of fluorescence in OH mixtures. A, a graph A: fluorescent emission of compound TPC-CH3Spectrum (fw =0% -90%); FIG. B shows the trend of fluorescence change (inset: photographs fw of the solution under a 365nm UV lamp are 0%, 20%, 40%, 60%, 80%, respectively).
FIG. 3 is a fluorescence spectrum of the interaction of the compound prepared in example 1 of the present invention as a fluorescent probe with different nitroaromatic compounds.
FIG. 4 is a PL profile of the interaction of the compound prepared in example 1 of the present invention as a fluorescent probe with nitroaromatic compounds of varying concentration gradients.
FIG. 5 is a fluorescence spectrum of competitive assay of nitroaromatic compound with the compound prepared in example 1 of the present invention as a fluorescent probe.
FIG. 6 is a photograph of the compound prepared in example 2 of the present invention 1 H NMR spectrum.
FIG. 7 shows the compound prepared in example 2 of the present invention in THF/C 2 H 5 Fluorescence spectra and trend plots of fluorescence in OH mixtures. FIG. A: compound TPC-NH 2 Fluorescence emission spectrum (fw =0% -90%); FIG. B shows the trend of fluorescence change (inset: photographs fw of the solution under a 365nm UV lamp are 0%, 20%, 40%, 60%, 80%, respectively).
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
The carbazole derivative with AEE characteristic, TPC-CH 3 The preparation method comprises the following steps in sequence:
4- (9H-carbazol-9-yl) phenylboronic acid (1.32g, 4.59mmol), 2,4,6-tribromotoluene (0.5g, 1.53mmol), anhydrous potassium carbonate (1.75g, 12.7mmol), pd (PPh) 3 ) 4 (0.1g, 0.087 mmol) was placed in a three-necked flask, and 125mL of 1, 4-dioxane and 25mL of distilled water were added thereto, stirred and heated to 90 ℃ under nitrogen, and reacted for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with 50mL of distilled water and 30mL of methylene chlorideDrying the mixture with anhydrous sodium sulfate, filtering, and spinning out the solvent. Purification by column chromatography using petroleum ether/dichloromethane (20/1,v/v) as eluent, recrystallization from dichloromethane and n-hexane gave 0.99g of a white powder, yield: 79.11 percent.
The compound TPC-CH prepared 3 Is/are as follows 1 The H NMR spectrum is shown in figure 1, and the structural formula is as follows:
experiment 1: AEE performance experiments of the compounds prepared in example 1.
Although the compounds are highly soluble in most organic solvents, many substances are not soluble in ethanol. To examine the AEE activity of the compound prepared in example 1, ethanol was added to its THF solution to make up THF-C at various concentrations ranging from 0% to 90% by volume fraction 2 H 5 The PL spectrum of the OH solution, recorded mixture, is shown in figure 2. As shown in FIG. 2 (B), the compound TPC-CH 3 Strong fluorescence is emitted in pure THF solution, the fluorescence intensity is gradually enhanced along with the increase of the ethanol content, and the emission intensity reaches the highest value when the ethanol content reaches 80 percent and is 5 times higher than the original value. The compounds are capable of emitting fluorescence in pure solution, while the fluorescence intensity in mixed solution is enhanced, which is characterized by a typical aggregation-induced enhanced emission (AEE) effect.
Experiment 2: TPC-CH 3 Interaction experiment between fluorescent probe and different nitro compounds
Probe TPC-CH 3 The fluorescence excitation wavelength of (2) is 300nm, the voltage is 400V, and the slit width is 5:5. The concentration is 10 by taking DMF as a solvent -5 M Probe solution 100. Mu.M Nitro-phenol (2-NP), M-nitrophenol (3-NP), 4-chloronitrobenzene (4-CNB), o-dinitrobenzene (1,2-DNB), M-dinitrobenzene (1,3-DNB), p-dinitrobenzene (1,4-DNB), 2,4-dinitrochlorobenzene (2,4-DNT), 4-nitrobenzaldehyde (4-NBA), phloroglucinol (M-THB) and 2,4,6-Trinitrophenol (TNP) were added as analytes to the sensor T separatelyPC-CH 3 In (1). As shown in FIG. 3, the fluorescence intensity is reduced sharply only when TNP is added, while the fluorescence intensity of other nitro compounds is reduced to a small extent but the quenching degree is far less than that of TNP, which indicates that the sensor TPC-CH 3 Is selective for TNP.
Experiment 3: TPC-CH 3 Interaction experiment of TNP as fluorescent probe and different concentration gradients
To determine the response of the probe solution to different kinds of nitroaromatic compounds under a concentration gradient, the experiment was carried out at 10 -5 The probe solution of M is added with nitro compounds (0,10,20, … … μ M) with different concentrations, as shown in FIG. 4, the probe has weak response to 2-NP and 1,4-DNB and small amplitude is increased with increasing concentration, but the response degree is far lower than that of the probe to TNP, the fluorescence intensity of the probe is obviously increased along with increasing concentration of TNP in a gradient manner, and the Detection limit is calculated to be 0.305 μ M by the formula Detection limit =3 σ/K (wherein σ is the standard deviation when TNP is not added, and K is the slope of the linear relation between the fluorescence intensity of the sensor and the concentration of TNP). The sensor TPC-CH can be seen in contrast to the reported detection limits of TNP for various sensors 3 The detection limit is lower, and the detection effect on TNP is better. All above can prove the compound TPC-CH 3 Can be used as a fluorescent probe to effectively and selectively recognize TNP. The detection limits of the various sensors are compared as follows:
experiment 4: TPC-CH 3 Interference experiment
This experiment added TNP at a concentration of 100. Mu.M to another nitro compound at 200. Mu.M to investigate whether the other nitro compound would have an effect on TNP. As can be seen from FIG. 5, the sensor is quenched by TNP despite the existence of other nitro compounds in larger concentration, which shows that the other nitro compounds have little influence on TNP, and the sensor has strong anti-interference capability.
Experiment 5: TPC-CH 3 Study of thermal stability
By Py synthesisDetermination of TPC-CH by thermal analyzer 3 The test uses nitrogen atmosphere, the scanning speed is 10 ℃/min, and the scanning range is 100-800 ℃. TPC-CH as shown in Table 1 (Table 1 is a thermal analysis data table of the compound prepared in example 1 of the present invention) 3 Has a glass transition temperature (Tg/. Degree.C.) of up to 237 ℃; compound TPC-CH 3 The thermal decomposition temperature of the compound was determined as the temperature at which 10% of its weight loss occurred, and reached 525 ℃. The above data indicate that the compounds have relatively high glass transition temperatures and thermal decomposition temperatures.
Table 1 thermal analysis data for the compounds
Tab.1 Thermal analysis data for the compound
Experiment 6: TPC-CH 3 Study of photophysical Properties of
The ultraviolet absorption spectrum and the fluorescence emission spectrum of the compound were measured at room temperature. The voltage of the fluorescence emission spectrum was 400V, the excitation wavelength was 300nm, and the slit width was 5:5. Table 2 shows the ultraviolet absorption data, fluorescence emission data, and absolute quantum yield of the compound prepared in example 1 of the present invention. As can be seen from Table 2, TPC-CH with AEE effect 3 In the solid state, the absolute quantum yield reaches 23.03 percent, which shows that the luminescent material has good luminescent effect.
Table 2 spectral data of the compounds
Tab.2 Spectral data of compounds
The results show that: experiments 1,2, 3 and 4 can prove that TPC-CH 3 As a fluorescent probe, the fluorescent probe not only can efficiently and specifically detect TNP, but also has strong anti-interference performance, and with the addition of TNP, a probe solution has a fluorescence quenching phenomenon, but does not have obvious peak shape change, so that the probe solution is inferred to be dynamic quenchingStrongly electron withdrawing structure of TNP, TPC-CH 3 Such that TNP and TPC-CH 3 The probes lose their excitation energy by a charge transfer mechanism and fall to a ground state, resulting in fluorescence quenching. Experiments 5 and 6 can prove that the compound with the AEE effect has a development prospect as an OLED material.
Example 2:
the carbazole derivative having AEE characteristics of the present invention, TPC-NH 2 The preparation method comprises the following steps in sequence:
4- (9H-carbazol-9-yl) phenylboronic acid (1.31g, 4.55mmol), 2,4,6-tribromoaniline (0.5g, 1.52mmol), anhydrous potassium carbonate (1.75g, 12.7mmol), pd (PPh) 3 ) 4 (0.1 g,0.087 mmol) was placed in a two-necked flask, and 125mL of DMSO and 25mL of distilled water were added thereto, stirred and heated to 100 ℃ under nitrogen, and reacted for 24 hours. After the reaction, the reaction mixture was cooled to room temperature, extracted with 50mL of distilled water and 30mL of dichloromethane, dried over anhydrous sodium sulfate, filtered under suction, and the solvent was removed by evaporation. Column chromatography purification using petroleum ether/ethyl acetate (100/2.5, v/v) as eluent, recrystallization from dichloromethane and absolute ethanol gave 0.92g of pale yellow powder, yield: 74.34 percent.
Preparation of the compound 1 The H NMR spectrum is shown in FIG. 6, and the structural formula is as follows:
experiment 1: to investigate whether the compound prepared in example 2 has AEE properties, an ethanol solution was also added to the THF solution of the compound to prepare THF-C solutions with different volume fractions 2 H 5 The OH solution, as shown in FIG. 7 (B), can emit fluorescence, the compound in the original THF solution gradually increases in aggregation degree with the increase of ethanol content, the fluorescence intensity also increases, the highest fluorescence intensity is 8.3 times higher than the original value when the ethanol content reaches 80%, and the fluorescence characteristic also accords with aggregation-induced enhanced emission (AEE) characteristics.
Experiment 2: TPC-NH 2 Thermal stability of (2)Is especially suitable for the treatment of diabetes
TPC-NH determination by Py Integrated thermal Analyzer 2 The test uses nitrogen atmosphere, the scanning speed is 10 ℃/min, and the scanning range is 100-800 ℃. TPC-NH as shown in Table 3 (Table 3 is a thermal analysis data table of the compound prepared in example 2 of the present invention) 2 Up to 241 ℃ glass transition temperature (Tg/. Degree.C.); compound TPC-NH 2 The thermal decomposition temperature of the compound was determined as the temperature at which 10% of the weight loss occurred, and reached 533 ℃. The above data indicate that the compounds have higher glass transition temperatures and thermal decomposition temperatures.
Thermal analysis data for the compounds of Table 3
Tab.3 Thermal analysis data for the compound
Experiment 3: TPC-NH 2 Study of photophysical properties of
The ultraviolet absorption spectrum and the fluorescence emission spectrum of the compound were measured at room temperature. The voltage of the fluorescence emission spectrum was 400V, the excitation wavelength was 300nm, and the slit width was 5:5. Table 4 shows uv absorption data, fluorescence emission data, and absolute quantum yield table of the compound prepared in example 2 of the present invention. As can be seen from Table 4, TPC-NH having AEE effect 2 In a solid state, the absolute quantum yield reaches 26.79 percent, which shows that the luminescent material has good luminescent effect.
Table 4 spectral data of the compounds
Tab.4 Spectarl data of compounds
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (3)
1. A carbazole derivative with AEE characteristics is characterized in that the carbazole derivative has a structural formula shown as a formula I:
wherein R is selected from-NH 2 and-CH 3.
2. The process for preparing carbazole derivatives with AEE characteristics according to claim 1, wherein the synthetic route is as follows
The preparation method specifically comprises the following steps:
will be provided with
4- (9H-carbazol-9-yl) phenylboronic acid, anhydrous potassium carbonate and Pd (PPh) 3 ) 4 Placing the mixture into a two-neck bottle, adding 1,4-dioxane or DMSO and distilled water into the two-neck bottle, stirring and heating the mixture to 90-100 ℃ under the protection of nitrogen, and reacting for 24 hours. (ii) a Cooling to room temperature after the reaction is finished, extracting with distilled water and dichloromethane, drying with anhydrous sodium sulfate, performing suction filtration, and spinning out the solvent; purifying by column chromatography with petroleum ether/ethyl acetate as eluent, and recrystallizing with ethanol to obtain crystal or powder.
3. The application of the carbazole derivative with AEE characteristic prepared by the preparation method according to claim 2 as a fluorescent probe for identifying small molecular substances is characterized by being specifically applied as a fluorescent probe for identifying 2,4,6-trinitrophenol.
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| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
| CN113248391A (en) * | 2021-05-26 | 2021-08-13 | 辽宁师范大学 | Benzidine compound with AIE characteristic, preparation method and application |
| CN113336622A (en) * | 2021-04-09 | 2021-09-03 | 辽宁师范大学 | Fluorene derivative with AIE characteristic, preparation method and application |
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| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
| CN113336622A (en) * | 2021-04-09 | 2021-09-03 | 辽宁师范大学 | Fluorene derivative with AIE characteristic, preparation method and application |
| CN113248391A (en) * | 2021-05-26 | 2021-08-13 | 辽宁师范大学 | Benzidine compound with AIE characteristic, preparation method and application |
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