CN113248391A - Benzidine compound with AIE characteristic, preparation method and application - Google Patents

Benzidine compound with AIE characteristic, preparation method and application Download PDF

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CN113248391A
CN113248391A CN202110575848.7A CN202110575848A CN113248391A CN 113248391 A CN113248391 A CN 113248391A CN 202110575848 A CN202110575848 A CN 202110575848A CN 113248391 A CN113248391 A CN 113248391A
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benzidine
rare earth
deionized water
aie
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CN113248391B (en
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闫杰
王嘉琪
惠天琦
赵龙炫
黄欣桐
马悦然
李昕
徐弋斐
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Liaoning Normal University
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Abstract

The invention discloses a benzidine compound with AIE effect, which has the following structural formula:
Figure 97936DEST_PATH_IMAGE002
the R = -CHO, -COOH and-NO2、‑NH2、‑OCH3、‑CH3、‑C2H5、‑CF3or-CCl3Can be used as a fluorescent probe for identifying rare earth ions, particularly rare earth metal ions Ho3+Has high-efficiency specificity recognition.

Description

Benzidine compound with AIE characteristic, preparation method and application
Technical Field
The invention relates to a series of aggregation-induced emission (AIE) materials, in particular to a benzidine compound with AIE characteristics, a preparation method and application thereof.
Background
The phenomenon that the more aggregated fluorescence is stronger is aggregation induced luminescence effect, called AIE effect for short. The compound having the AIE effect hardly emits fluorescence in a dispersed state, emits strong fluorescence after aggregation, and can emit fluorescence in a solid state in general. At present, Aggregation Induced Emission (AIE) materials are used for chemical probes and biological probes, and can be generally used for detecting substances such as biological small molecules, explosives and some metal ions.
Rare Earth Elements (REEs) include 17 metals: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), and yttrium (Y), which have similar physical and chemical properties. All rare earth elements are present in the soil in the form of salt minerals, most commonly phosphates and fluorocarbons. The rare earth metal ions have special electronic, optical and magnetic properties and play an important role in the fields of traditional industry, non-ferrous metal materials, high and new technology and the like. Rare earth metal elements constitute key components of many everyday electronic and technical devices, such as yttrium for ceramics, metal alloys and lasers; lanthanum is used in digital cameras and electric vehicle batteries; cerium is used for catalysts and optical glasses; europium is used in Liquid Crystal Displays (LCDs) and fluorescent lamps. The rare earth metal ions in proper amount also have certain benefits on human health, such as blood sugar level regulation and anticoagulation. Therefore, global demand for rare earth is rapidly increased, and detection of rare earth metal ions is also of great significance. The use of AIE type fluorescent probes for detecting rare earth metal ions has received more and more attention because of fewer reports.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a benzidine compound with AIE characteristics, a preparation method and application thereof.
The technical solution of the invention is as follows: an AIE-effective benzidine compound having the following structural formula:
Figure 843087DEST_PATH_IMAGE001
the R = -CHO, -COOH and-NO2、-NH2、-OCH3、-CH3、-C2H5、-CF3or-CCl3。
The preparation method of the benzidine compound with the AIE effect comprises the following synthetic route:
Figure 40850DEST_PATH_IMAGE002
the method comprises the following steps of:
will be provided with
Figure 57348DEST_PATH_IMAGE003
4-Triphenylamine borate, Pd (PPh)3）4And K3PO4Adding into a container containing DMSO and deionized water, and adding into a container containing DMSO and deionized water in the presence of N2Starting magnetic stirring under protection, heating in an oil bath, fully reacting and mixing, cooling to room temperature, adding deionized water, and extracting with dichloromethane; the organic layer was washed with deionized water and then with anhydrous Na2SO4Drying, evaporating the solvent, purifying the crude product by silica gel column chromatography with mixed solvent of petroleum ether/dichloromethane, and recrystallizing with n-hexane to obtain colorless flaky crystals, i.e. the target compound.
The application of the benzidine compound with the AIE effect as a rare earth metal ion fluorescent probe.
The benzidine compounds with the AIE effect are applied as rare earth metal ion fluorescent probes and holmium ion identification fluorescent probes.
The benzidine compound prepared by the invention has Aggregation Induced Emission (AIE) characteristics, can be used as a fluorescent probe for identifying rare earth metal ions, and particularly can be used for identifying rare earth metal ions Ho3+High-efficiency specificity recognition.
Drawings
FIG. 1 is a drawing of a compound prepared in example 1 of the present invention1H NMR spectrum.
FIG. 2 shows the compound prepared in example 1 of the present invention in THF/H2Fluorescence spectra and trend plots of fluorescence in O mixtures.
FIG. 3 is a fluorescence spectrum of a compound prepared in example 1 of the present invention in a tetrahydrofuran or xylene solution.
FIG. 4 is a fluorescence spectrum of the interaction of the compound prepared in example 1 of the present invention as a fluorescent probe with different rare earth metal ions.
FIG. 5 shows the compound prepared in example 1 of the present invention as a fluorescent probe and Ho with different concentration gradients3+Fluorescence spectra of the interaction.
Detailed Description
Example 1:
the preparation method of the benzidine compound with the AIE effect is sequentially carried out according to the following steps:
weighed 1,3, 5-triiodo-2, 4, 6-trimethylbenzene (1.00 g, 2.00 mmol), 4-triphenylamine borate (2.60 g, 9.00 mmol), Pd (PPh)3）4(0.20 g, 0.17 mmol) and K3PO4(3.00 g, 14.10 mmol) was added to a two-necked flask containing 30 mL of DMSO and 1 mL of deionized water. In N2Magnetic stirring was turned on under protection, the reaction was heated to 85 ℃ in an oil bath for 24 h, and after the reaction mixture was cooled to room temperature, 20 mL of deionized water was added and extracted with dichloromethane (3X 50 mL). The organic layer was washed with 100 mL deionized water and anhydrous Na2SO4Drying for 30 min, evaporating the solvent, and purifying the crude product by silica gel column chromatography using mixed solvent of petroleum ether and dichloromethane (4/1, v/v). Recrystallizing with n-hexane to obtain colorless flaky crystal as the compound.
Preparation of the compound1The H NMR spectrum is shown in figure 1, and the structural formula is as follows:
Figure 961850DEST_PATH_IMAGE004
experiment:
experiment 1: AIE Performance test of the Compound (hereinafter referred to simply as Compound) prepared in example 1
The compounds being in different H2Volume fraction of O: (f wVol%) of H2Fluorescence property test is carried out in the O/THF mixed solution. According to H2THF-H with different concentrations is prepared from 0-99% of O volume fraction2The fluorescence spectrum (A) and the trend graph (B) are shown in FIG. 2. With H2The O volume fraction continues to increase, as does the degree of aggregation of the fluorescer in solution. The volume fraction of water is in the range of 0% to 50% and the fluorescence of the compound is barely detectable by the fluorescence spectrum. When in usef wFluorescence quantum yield (Φ) of compound at = 0%F) It was 0.08%. However, whenf wAt 60% or more, the fluorescence intensity of the compound rapidly increases, and the maximum emission wavelength appears at 368 nm. When in usef w(ii) when 99%, the fluorescence intensity of the compound is aboutf w60 times of = 0%, corresponding fluorescence quantum yield (Φ)F) 13.60% is 170 times the fluorescence quantum yield in pure THF. With followingf wFrom 0% to 99%, the maximum is gradually red-shifted from 361 nm to 370 nm. The compounds were dissolved in tetrahydrofuran or xylene solution and their emission spectra were collected, the fluorescence spectra of which are shown in figure 3, and the experimental results show that the maximum emission wavelength of the compounds appears to be about 15 nm across as the polarity of the solvent increases.
Experiment 2: interaction experiment of compound serving as fluorescent probe and different rare earth metal ions
Adding 100 μ M La to the compound respectively3+、Eu3+、Gd3+、Dy3+、Ho3+、Tm3+、Lu3+、Pr3+8 kinds of rare earth goldBelongs to ions, and the fluorescence spectrum of the ions is tested, and the fluorescence spectrum is shown in figure 4. The results show that: the fluorescence intensity of the 8 rare earth metal ions to the compound is improved to different degrees, but Ho is added3+When the fluorescence intensity was significantly increased.
Experiment 3: compound as fluorescent probe and Ho with different concentration gradients3+Interaction experiments
Compound pair Ho with different concentrations of 0-10 and 20 … … 100 mu M3+The results of the fluorescence performance test are shown in FIG. 5.
Results display Ho3+The concentration has good linear relation with the fluorescence enhancement of the compound
Example 2:
the preparation method of the benzidine compound with the AIE function sequentially comprises the following steps:
weighed 1,3, 5-triiodo-2, 4, 6-triethylbenzene (1.00 g, 2.00 mmol), 4-triphenylamine borate (2.60 g, 9.00 mmol), Pd (PPh)3）4(0.20 g, 0.17 mmol) and K3PO4(3.00 g, 14.10 mmol) was added to a two-necked flask containing 30 mL of DMSO and 1 mL of deionized water. In N2Magnetic stirring was turned on under protection, the reaction was heated to 85 ℃ in an oil bath for 24 h, and after the reaction mixture was cooled to room temperature, 20 mL of deionized water was added and extracted with dichloromethane (3X 50 mL). The organic layer was washed with 100 mL deionized water and anhydrous Na2SO4Drying for 30 min, evaporating the solvent, and purifying the crude product by silica gel column chromatography using mixed solvent of petroleum ether and dichloromethane (4/1, v/v). Recrystallizing with n-hexane to obtain colorless flaky crystal as the compound.
The structural formula of the prepared compound is as follows:
Figure 671180DEST_PATH_IMAGE005
example 3:
the preparation method of the benzidine compound with the AIE function sequentially comprises the following steps:
weighing 1,3, 5-triiodide-2,4, 6-triaminobenzene (1.00 g, 2.00 mmol), 4-triphenylamine borate (2.60 g, 9.00 mmol), Pd (PPh)3）4(0.20 g, 0.17 mmol) and K3PO4(3.00 g, 14.10 mmol) was added to a two-necked flask containing 30 mL of DMSO and 1 mL of deionized water. In N2Magnetic stirring was turned on under protection, the reaction was heated to 85 ℃ in an oil bath for 24 h, and after the reaction mixture was cooled to room temperature, 20 mL of deionized water was added and extracted with dichloromethane (3X 50 mL). The organic layer was washed with 100 mL deionized water and anhydrous Na2SO4Drying for 30 min, evaporating the solvent, and purifying the crude product by silica gel column chromatography using mixed solvent of petroleum ether and dichloromethane (4/1, v/v). Recrystallizing with n-hexane to obtain colorless flaky crystal as the compound.
The structural formula of the prepared compound is as follows:
Figure 356239DEST_PATH_IMAGE006

Claims (4)

1. a benzidine compound having an AIE effect, characterized by the following structural formula:
Figure 67517DEST_PATH_IMAGE002
the R = -CHO, -COOH and-NO2、-NH2、-OCH3、-CH3、-C2H5、-CF3or-CCl3。
2. A process for producing the benzidine compound having AIE effect according to claim 1, which comprises the steps of:
will be provided with
Figure 187919DEST_PATH_IMAGE004
4-Triphenylamine borate, Pd (PPh)3）4And K3PO4Adding intoIn a vessel with DMSO and deionized water, in N2Starting magnetic stirring under protection, heating in an oil bath, fully reacting and mixing, cooling to room temperature, adding deionized water, and extracting with dichloromethane; the organic layer was washed with deionized water and then with anhydrous Na2SO4Drying, evaporating the solvent, purifying the crude product by silica gel column chromatography with mixed solvent of petroleum ether/dichloromethane, and recrystallizing with n-hexane to obtain colorless flaky crystals, i.e. the target compound.
3. Use of the benzidine-based compound having AIE effect according to claim 1 as a fluorescent probe for rare earth metal ions.
4. The use of the benzidine-based compound having the AIE effect as a fluorescent probe for rare earth metal ions according to claim 3, which is characterized by being used as a fluorescent probe for identifying holmium ions.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN115594629A (en) * 2022-09-20 2023-01-13 辽宁师范大学（Cn） Carbazole derivative with AEE characteristic and preparation method and application thereof

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CN108358843A (en) * 2018-03-29 2018-08-03 天津农学院 A kind of organic compound and application for detecting water environment Rare Earth Ion content

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CN108358843A (en) * 2018-03-29 2018-08-03 天津农学院 A kind of organic compound and application for detecting water environment Rare Earth Ion content

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Title
LIFANG ZHAO: "Rational bridging affording luminogen with AIE features and high field effect mobility", 《J.MATER.CHEM.C》 *
XUEJUN ZHAN等: "Benzene-cored AIEgens for deep-blue OLEDs:high performance without hole-transporting layers,and unexpected excellent host for orange emission as a side-effect", 《CHEM.SCI.》 *

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CN115594629A (en) * 2022-09-20 2023-01-13 辽宁师范大学（Cn） Carbazole derivative with AEE characteristic and preparation method and application thereof

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