CN115785153B - Binuclear cuprous cluster luminescent material mixed with nitrogen and phosphine and fluorescence sensing thereof - Google Patents
Binuclear cuprous cluster luminescent material mixed with nitrogen and phosphine and fluorescence sensing thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 132
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 8
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 claims abstract description 136
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000004044 response Effects 0.000 claims abstract description 44
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003446 ligand Substances 0.000 claims abstract description 33
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 23
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a binuclear cuprous cluster luminescent material compounded by nitrogen/phosphine ligands, a preparation method thereof and VOC sensing application of the material; the structural formula of the luminescent material is (Xantphos) Cu 2I2(3-PhPy)2, wherein Xantphos is electrically neutral biphosphine ligand 4, 5-bis (diphenylphosphine) -9, 9-dimethyl xanthene, and 3-PhPy is nitrogen-containing ligand 3-phenylpyridine; the CuI-ligand complex is prepared by carrying out a coordination reaction on the CuI and the ligand through mechanical ball milling; the material itself has strong luminescence, and can be used as luminescent material; after the material is placed in pyridine or cyclohexylamine atmosphere, different fluorescence sensing responses of maximum luminous intensity deviation or fluorescence quenching are respectively presented; the material is easy to prepare, has good solubility and stability, is also easy to prepare into a paper-based load or polymer doped fluorescent sensing film, and the film also has rapid and selective response and sensitive identification fluorescent sensing performance.
Description
Technical Field
The invention relates to the technical field of luminescent materials, relates to the field of photoluminescent materials, and particularly relates to the field of fluorescent sensing materials.
Background
Volatile organic compounds (Volatile Organic Compound) are short for VOC, and are important components of atmospheric pollution. The sources are rich, the varieties are various, and most of the materials are toxic and harmful substances, prolonged exposure to VOC atmospheres can cause harm to human health. However, due to the low concentration of VOCs in the environment, the volatilization is slow and the symptoms are not easily perceived, so that the detection of VOCs remains difficult.
Along with the rapid development of socioeconomic performance, various pollution is increasingly aggravated. For example, industrial exhaust emission pollution, and various building and finishing materials used in large quantities in the residential industry, all cause problems of air pollution. VOC is a main factor of indoor air pollution, and specific components of the VOC comprise benzene series, organic chloride, freon series, pyridine compounds and the like, and sources of the VOC are mainly paint, wallpaper, floor tile, heat insulating material, adhesive and the like in the aspects of indoor decoration materials and furniture. To understand the VOC status of air, it is important to detect it. The existing methods are as follows: gas Chromatography (GC), high Performance Liquid Chromatography (HPLC), electrochemical sensing, atomic absorption spectrometry, and the like. However, these methods have some short points, such as complicated instruments, difficult carrying, complicated procedures, high cost, overlong detection time, sample consumption, secondary pollution and the like.
Fluorescent sensing detection methods are becoming increasingly important relative to traditional detection methods. Because the fluorescence sensor has the advantages of high sensitivity, abundant collected signals, stable signals, easy miniaturization of the instrument, convenient use and the like, the development of the fluorescence sensor is steadily advancing in the direction of comprehensive and practical use. Fluorescent sensors are mainly divided into two categories: a thin film fluorescence sensor that is easily reusable and is responsive to gas phase material sensing, and a homogeneous fluorescence sensor for use in solution. The main structure of the fluorescent sensor is generally composed of the following three parts: a receptacle for a foreign substance, a reporter, and a connector. In the whole fluorescent sensor structure, the function of the receiver is responsible for the reception of foreign molecules and the conversion of signals. The choice and preparation process of the receiver material (i.e. the sensitive material) is critical and directly determines the performance and application range of the sensor.
Depending on the type of substance of the sensing material, the fluorescent sensor may be classified into a biological sensor, an inorganic material sensor, and an organic material sensor. But each has advantages and disadvantages. The biological material sensor generally uses enzymes, microorganisms and the like as sensing materials, is mainly applied to the fields of biology and medicine, and has less application in other fields. Inorganic materials are mainly used for sensing, such as semiconductor materials, metals and ceramics, and are generally used for pressure and temperature sensing, but due to the fact that the internal structure is too compact, the luminous center is hardly affected by external atmosphere, and the inorganic materials are rarely applied to gas and water source detection. Organic material sensors are gradually applied to VOC fluorescence sensing because of various organic molecular structures and properties, and convenience in design and optimization. However, fluorescence of organic materials is greatly affected by molecular stacking, and the phenomenon of aggregation-induced fluorescence quenching (ACQ) is the most prominent manifestation. In general, organic material sensors are still in the development stage.
According to the prior great amount of research reports, the complex can form a hybrid material with better stability through coordination hybridization of inorganic and organic materials and can exhibit fluorescence sensing function, so the complex is a better solution for organically combining the advantages of the inorganic materials and the organic materials. Wenger reviewed the vapor-induced color change of the complex and the application prospect of VOC sensing, and predicted that this was a simple and inexpensive solution (CHEMICAL REVIEWS 2013,113 (5), 3686-3733). However, as mentioned herein, researchers in this field generally only study the molecular mechanism of this phenomenon, and ignore the quantitative, inexpensive, etc. application requirements of actual sensing detection. The platinum and gold used by the reported complex are expensive, which limits the wide application, and compared with other metals, copper has the advantages of low price, environmental protection, no toxicity and the like, has abundant content in crust, and the copper resource reserve in China is the third place in the world. The existing research reports at present show that the cuprous complex is not only based on cheap metal, but also has good luminescence performance, and the luminescence performance (such as the regulation of luminescence wavelength, quantum yield and the like) can be regulated and controlled through a structure, so that the cuprous complex can be guessed as a molecular development platform for fluorescence sensing detection of the VOC with great prospect. The key problem at present is to find and develop a cuprous complex sensing material with the fluorescent response property of VOC, thereby promoting the wide application of the fluorescent sensing technology of VOC.
Disclosure of Invention
The invention aims to provide a novel binuclear cuprous cluster luminescent material, a preparation method and application thereof, and sensing application of the material to pyridine and cyclohexylamine VOC. The binuclear cuprous cluster complex luminescent material with good thermal stability is conveniently and cheaply prepared by carrying out coordination reaction on cuprous iodide and two ligands under the condition of mechanical ball milling, and the binuclear cuprous cluster complex luminescent material can be found to have rapid and selective obvious fluorescence response in pyridine and cyclohexylamine atmospheres and can be used for fluorescence sensing detection application.
According to one of the technical schemes, the invention provides a novel binuclear cuprous cluster luminescent material, which is obtained by carrying out coordination reaction on CuI, a chelating phosphine ligand Xantphos and a terminal nitrogen-containing ligand 3-PhPy under the condition of mechanical ball milling, wherein the molecular structure of the luminescent material is (Xantphos) Cu 2I2(3-PhPy)2, xantphos is an electrically neutral bisphosphine ligand 4, 5-bis (diphenylphosphine) -9, 9-dimethyl xanthene, and 3-PhPy is a nitrogen-containing ligand 3-phenylpyridine.
The binuclear cuprous cluster luminescent material is in a triclinic system, the space group of P-1 is provided, and the unit cell parameters are as follows α＝86.946(2)°，β＝77.009(2)°，γ＝86.351(2)°，Z=2, d C＝1.533g/cm3, the crystalline colour of the material being yellow; the material structure is represented as a binuclear neutral complex, two cuprous ions adopt different tetrahedral coordination modes, and a double tetrahedral structure connected by sharing two bridge group iodide ions is formed; one cuprous in the structure adopts a CuI 2P2 tetrahedral coordination mode, wherein two I are bridge iodide ions, and two P come from a biphosphine ligand Xantphos; the other cuprous in the structure adopts a CuI 2N2 tetrahedral coordination mode, wherein two I are bridge iodide ions, and two N are respectively from two nitrogen-containing ligands 3-PhPy; and there is stronger supermolecular action between adjacent molecules, wherein one is that two biphosphine ligands in the adjacent molecules form stronger intermolecular pi.pi.stacking action through benzene rings through C-H.pi.interaction between benzene rings and xanthene ring components, and the other is that two 3-PhPy ligands in the adjacent molecules form stronger intermolecular pi.pi.pi.stacking action through benzene rings, and the structural rigidity of the interior of the material is improved; the molecular structure is shown as formula (I):
the binuclear cuprous cluster luminescent material is characterized by being a broad-spectrum excitation high-efficiency luminescent fluorescent powder, and can emit strong green fluorescence under the excitation of ultraviolet light and visible light within the wavelength range of 250 to 450 nanometers, wherein the maximum luminescence wavelength is 540nm, and the color coordinate value is (0.3899,0.5280), so that the binuclear cuprous cluster luminescent material can be used as a photoluminescence green material or a luminescent layer green material in an electroluminescent device formed by multiple layers of organic materials.
The second technical scheme of the invention is to provide a preparation method of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2. The preparation method is realized by fully carrying out coordination reaction on CuI and ligand Xantphos and 3-PhPy under the condition of mechanical ball milling, and finally taking out to obtain product powder. The specific implementation scheme comprises four steps:
(1) Weighing CuI powder and powder of ligand Xantphos and 3-PhPy at room temperature, and adding into a ball milling tank;
(2) Adding ball grinding balls into a ball milling tank, wherein the ball-material ratio is 70:1, and then adding 3mL of acetonitrile;
(3) Putting the ball milling tank into a ball mill, setting the rotating speed of the ball mill to 160 revolutions per minute, and performing ball milling treatment for 4 hours;
(4) After ball milling, placing the ball milling tank in a vacuum oven for drying at 40 ℃, and obtaining powder which is a product;
(5) The molar ratio of the three reactants CuI to Xantphos is 3-PhPy and is 1:2:2, and the ball milling tank is an agate tank with the volume of 50 mL.
The third technical scheme of the invention is to provide a fluorescent sensing application of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2; after the luminescent material (Xantphos) Cu 2I2(3-PhPy)2 is placed in an environment containing pyridine VOC vapor, the maximum luminescence wavelength of the luminescent material (Xantphos) is obviously blue-shifted (the new maximum luminescence wavelength is 527 nm), and the luminescence is changed from original green to blue-green, so that the luminescent material can be used as a sensing material for detecting pyridine VOC.
The fourth technical scheme of the invention is to provide an application of a binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 fluorescent sensing film; after the fluorescent sensing film is placed in an environment containing pyridine vapor, the phenomenon that the maximum luminous wavelength is obviously blue shifted (the new maximum luminous wavelength is 527 nm) is rapidly presented, and the luminescence is changed from the original green to blue-green, so that the fluorescent sensing film can be used as a sensing film for detecting pyridine VOC; in addition, after the fluorescent sensing film is placed in an environment containing cyclohexylamine vapor, the fluorescent sensing film can quickly show a remarkable response effect of fluorescence quenching, and the fluorescent sensing film does not show remarkable fluorescence response behaviors for various VOC vapors such as triethylamine, trimethylamine, ethanolamine, monomethylamine, benzene, 2-phenylpyridine, 3-phenylpyridine, 2-aminopyridine, 4-hydroxypyridine, diethylenetriamine, ammonia water and the like, so the fluorescent sensing film can also be used as a selective fluorescent sensing film for detecting cyclohexylamine VOC.
The fifth technical scheme of the invention is to provide a preparation method of a binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 fluorescent sensing film. The preparation method is realized by dissolving binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 and coating the solution on a cellulose film. The specific implementation scheme comprises four steps:
(1) Dissolving luminescent material (Xantphos) Cu 2I2(3-PhPy)2 powder in dichloromethane at room temperature;
(2) The cellulose film is manufactured into a shape which is required to be conveniently applied, and the shape is used as test paper base paper;
(3) Coating the luminescent material (Xantphos) Cu 2I2(3-PhPy)2 solution on test paper base paper at room temperature;
(4) And finally, drying the coated test paper under a vacuum condition, and obtaining the paper-based fluorescent sensing film after drying.
The sixth technical scheme of the invention is to provide a preparation method of a binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 doped fluorescent sensing film. The method is realized by embedding binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 into PMMA (polymethyl methacrylate), and the specific implementation scheme comprises four steps:
(1) Dissolving PMMA solid in dichloromethane at room temperature;
(2) Dissolving luminescent material (Xantphos) Cu 2I2(3-PhPy)2 powder in dichloromethane at room temperature;
(3) Mixing the two solutions, and stirring to fully react to obtain a clear solution A;
(4) And spin-coating the clear solution A on a quartz plate, a metal substrate or a base such as test paper base paper at room temperature, and drying to obtain the doped fluorescent sensing film.
The invention has the beneficial effects that firstly, the provided binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2, the introduced large-volume chelating phosphine ligand Xantphos and phenylpyridine-based nitrogen ligand 3-PhPy and the existence of the rigid Cu 2I2 binuclear cuprous iodide cluster core are beneficial to the luminescence of a molecular excited state, the quantum chemical calculation shows that the luminescence of the material comes from the charge transfer excited state from the cluster core to the nitrogen-containing ligand, the charge separation characteristic of the excited state is obvious, and the problem of the distortion of the excited state configuration commonly existing in cuprous complexes is effectively avoided, so that the luminescent material is beneficial to the luminescence of the material; in addition, strong supermolecular action exists between adjacent molecules in the material structure, and the supermolecular action increases the structural rigidity of the interior of the material, so that the molecular structure shows good fluorescence emission performance, and a foundation is provided for subsequent sensing performance research; the complex material has the advantages of low cost and easiness in purification, has good solubility and thermal stability, and provides technical support for further application of the material.
The invention has the beneficial effects that the fluorescence sensing application of the binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 with selective response to pyridine is performed, and the response is completed rapidly in a short time; the luminescent material has good fluorescence performance after responding to pyridine, and a very small amount of material powder can emit strong fluorescence, so that a small amount of fluorescent powder is needed in practical application, the application cost is reduced conveniently, and a doping way easy to operate is convenient for controlling the application cost; the sensing response characteristics of the material prepared by the same process can be observed and changed in color quickly after the material is placed in pyridine atmosphere; and the solubility and stability of the fluorescent material are good, so that the fluorescent material is convenient to use as a fluorescent sensing material.
The invention has the beneficial effects that the fluorescence sensing application of the binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 with selective response to cyclohexane is realized, and the response is completed rapidly in a short time; the fluorescence energy of the luminescent material after the response to the cyclohexylamine is completely quenched, the quenching degree is directly related to the quantity of the cyclohexylamine, the quenching response performance has good reversibility, the material and the sensor are easy to reuse, and the application cost control is also convenient; the sensing response characteristic of fluorescence quenching can be observed quickly after the material prepared by the same process is placed in the cyclohexane atmosphere; and the fluorescent sensing material has good solubility, stability and reversible response performance, and is convenient to use as the fluorescent sensing material.
The invention has the beneficial effects that the provided binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 is used for VOC sensing of the paper-based fluorescent film, the paper-based fluorescent film is as simple and convenient as a common gas detection test paper, when the paper-based fluorescent film is specifically used, after being placed in the environment existing in pyridine or cyclohexylamine atmosphere for a short time, the film is irradiated by an ultraviolet light source, the phenomenon that fluorescence is enhanced and color change/fluorescence quenching occurs rapidly can be observed, and the increase of VOC concentration shows the fluorescence response effect of intensity dependence, and shows the reversible rapid response and the fluorescence sensing performance of sensitive identification, so the paper-based fluorescent film can be used as a portable fluorescent detection test paper device for detecting VOC; the fluorescent sensing film can be flexibly manufactured into various required shapes, has light weight, is very convenient to carry and easy to prepare, and provides technical support for further application of luminescent materials.
The invention has the beneficial effects that the provided double-core cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 doped fluorescent film is applied to VOC sensing, the doped fluorescent film can be manufactured on various substrates such as quartz, plastic, paper and the like, or can be directly coated on an optical fiber port to be manufactured into an optical fiber sensing probe, when the invention is applied specifically, after the doped film is placed in the environment existing in pyridine or cyclohexylamine atmosphere for a short time, the film is irradiated by an ultraviolet light source, the phenomena of fluorescence enhancement and color change/fluorescence quenching can be observed, the increase of the VOC concentration shows the fluorescence response effect of intensity dependence, and the reversible rapid response and the fluorescence sensing performance of sensitive identification are shown, so the doped film can be used as a sensitive film component of an optical fiber sensor and the like for VOC detection.
The invention has the beneficial effects that finally, the method for preparing the binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 and the sensing film thereof has the advantages of simple and convenient process, simple and easily obtained equipment, low-cost and easily obtained raw materials 3-PhPy, low production cost, high material preparation yield, easy popularization, capability of obtaining a large number of products in a short time, and the like.
Drawings
FIG. 1. Crystallographic independent unit structure of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2.
FIG. 2 shows a structure diagram of a supramolecular dimer of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 molecules.
FIG. 3 is a diagram showing the stacking of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 molecules in unit cell and the surrounding space.
Fig. 4X-ray powder diffraction pattern of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2: (a) A spectrum obtained by simulation was calculated for the single crystal structure data according to example 2; (b) is a spectrum of the powder obtained in example 1 of the present invention.
FIG. 5 is a chart showing infrared absorption (FTIR) spectra of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2.
FIG. 6 ultraviolet-visible (UV-Vis) absorption spectra of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2.
FIG. 7 shows a fluorescence emission (PL-EM) spectrum of a polycrystalline powder of binuclear cuprous-cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 under 365nm ultraviolet excitation.
FIG. 8 shows fluorescence excitation (PL-EX) spectrum of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 polycrystal powder under the monitoring wavelength of 645nm of emitted light.
Fig. 9 shows a front-line orbital diagram of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 molecule, which clearly shows the charge transfer characteristic from cluster core to nitrogen-containing ligand.
FIG. 10 is a graph showing fluorescence emission spectra of a paper-based film loaded with binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 before and after a certain time of response in pyridine atmosphere; in the figure, s represents time unit seconds, and min represents time unit minutes.
Fig. 11 is a graph showing the shift (blue shift) of fluorescence emission wavelength during the response of a paper-based film loaded with binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 in pyridine atmosphere.
FIG. 12 is a graph showing the change spectrum of fluorescence emission intensity of a polymer-based binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 after a certain time of response in a cyclohexane atmosphere; in the figure, s represents time unit seconds, and min represents time unit minutes.
FIG. 13 is a graph showing the time dynamics of fluorescence quenching process of a polymer-based doped binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 in the cyclohexane atmosphere response process.
FIG. 14 is a graph showing the selective recognition response, i.e., selective fluorescence quenching response, of a polymer-based doped binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 to cyclohexylamine in various VOC atmospheres.
FIG. 15 is a graph showing the response of fluorescence enhancement of polymer-based doped binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 in pyridine atmosphere with different concentrations and the working curve obtained by fitting the response.
FIG. 16 is a graph showing the fluorescence quenching response of polymer-based doped binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 in pyridine atmosphere with different concentrations and the working graph obtained by fitting the same.
FIG. 17 is a graph showing the fluorescence quenching response of a polymer-based doped binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 in cyclohexylamine atmosphere with different concentrations and the working graph obtained by fitting the same.
Detailed Description
The implementation process and the material performance of the invention are illustrated by the examples:
example 1
The polycrystalline powder of the binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 is prepared by taking Xantphos, cuprous iodide and 3-PhPy as raw materials according to the following method: weighing 0.3mmol of Xantphos, 0.6mmol of cuprous iodide and 0.6mmol of 3-PhPy, placing into a ball milling tank, placing 17g of ball milling balls into the ball milling tank, respectively adding 8 big balls and 14 small balls with diameters of 10mm and 6mm, and then adding 3ml of acetonitrile as a liquid grinding aid. Ball milling for 4 hours at a rotational speed of 160rad/min in a ball mill; and (3) ball milling, and drying in a vacuum oven at 40 ℃ to obtain the product polycrystalline powder, wherein the yield (calculated by cuprous iodide) is 79.18%. After the complex luminescent material is placed in pyridine atmosphere for response, the fluorescence emission can be rapidly observed to be changed from green to blue-green.
Example 2
Synthesizing a monocrystal of a binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2: dissolving the complex powder in dichloromethane, dripping the solution into a test tube, slowly adding n-hexane as a precipitator, generating milky delamination at the interface, sealing a sample with a preservative film and a sealing film, and placing the sample in a sample rack, wherein a large number of yellow granular crystals are obtained in the test tube after a few days. A single yellow granular crystal 0.42mm X0.32 mm X0.20 mm in size was selected for X-ray single crystal structure testing. The molecular structure of the compound is shown in fig. 1 and 2, and the unit cell stacking structure is shown in fig. 3.
A series of tests were performed on pure phase crystal samples of binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2. The steady-state fluorescence test is carried out on the crystal sample of the material, and the result shows that the material can emit strong green light under the action of different excitation wavelengths within the wavelength range of 250 to 450 nanometers, the color coordinate value is 0.3899,0.5280, and the specific excitation spectrum and the specific emission spectrum are shown in the accompanying figures 7 and 8. It can be used as green luminescent material excited by various wavelengths, or as luminescent layer green luminescent material in electroluminescent device composed of multiple layers of organic materials.
Example 3
Preparation of a fluorescent sensing film loaded with binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 and atmosphere response thereof: 0.045g of luminescent material (Xantphos) Cu 2I2(3-PhPy)2 was weighed out and dissolved completely in 7mL of dichloromethane, and the solution was clear and transparent as a pale orange color and filtered. The cellulose film is manufactured into a size and a shape suitable for application by cutting and other methods, and is used as test paper base paper in the subsequent process; a proper amount of filtrate is taken, and the filtrate is coated on the base paper of the test paper by a printing, dip-coating or brush-coating method; drying the coated test paper under vacuum (60 ℃ for 30 min), and obtaining a fluorescence sensing film (fluorescence test paper) after the drying is completed; the sensing film was then placed into a VOC for response and fluorescence spectra were tested. As a result, it was found that the fluorescent sensor film, after being placed in an environment containing pyridine vapor, exhibited a phenomenon of blue shift in maximum emission wavelength (a new maximum emission wavelength of 527 nm) rapidly, and the luminescence was changed from the original green to blue-green, and thus was useful as a sensor film (test paper) for detecting pyridine VOCs; in addition, after the fluorescent sensing film is placed in an environment containing cyclohexylamine vapor, the fluorescent sensing film can quickly show a remarkable response effect of fluorescence quenching, and the paper-based fluorescent sensing film does not show remarkable fluorescence response behaviors for various VOC vapors such as triethylamine, trimethylamine, ethanolamine, monomethylamine, 2-phenylpyridine, 3-phenylpyridine, 2-aminopyridine, diethylenetriamine, diisopropylamine and ammonia water, so the paper-based fluorescent sensing film can also be used as a selective fluorescent sensing film (test paper) for detecting cyclohexylamine VOC. (see FIGS. 10 and 11).
Example 4
Preparation of a polymer-based binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 fluorescent sensing film and atmosphere response thereof: 0.8g of PMMA (polymethyl methacrylate, glass transition temperature: 105 ℃) was weighed out and dissolved completely in 9mL of methylene chloride, and the solution was colorless, clear and transparent. 0.040g of luminescent material (Xantphos) Cu 2I2(3-PhPy)2 was dissolved completely in 6mL of dichloromethane and the solution was pale green, clear and transparent. The luminescent material solution is slowly introduced into the PMMA solution, and the solution is clear and transparent. Spin-coating (1200 rad/min), drying (60 ℃ C., 30 min) and then placing into VOC for response on a clean quartz plate, and testing fluorescence spectrum. As a result, it was found that the fluorescent sensing film, after being placed in an environment containing pyridine vapor, rapidly exhibited a blue shift phenomenon of the maximum emission wavelength (the new maximum emission wavelength is 527 nm), and the emission was changed from the original green to blue-green, so that it was useful as a sensing film for detecting pyridine VOCs; in addition, after the fluorescent sensing film is placed in an environment containing cyclohexylamine vapor, the fluorescent sensing film can quickly show a remarkable response effect of fluorescence quenching, and the fluorescent sensing film does not show obvious fluorescence response behaviors for various VOC vapors such as triethylamine, trimethylamine, ethanolamine, monomethylamine, 2-phenylpyridine, 3-phenylpyridine, diethylenetriamine, diisopropylamine, ammonia water and the like, so that the fluorescent sensing film can also be used as a selective fluorescent sensing film for detecting cyclohexylamine VOC. (see fig. 12, 13, 14, 15, 16).
Example 5
Preparation of a polymer-based binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 fluorescent sensing film and atmosphere response thereof: 0.8g of PMMA (polymethyl methacrylate, glass transition temperature: 105 ℃) was weighed out and dissolved completely in 9mL of methylene chloride, and the solution was colorless, clear and transparent. 0.040g of luminescent material (Xantphos) Cu 2I2(3-PhPy)2 was dissolved completely in 6mL of dichloromethane and the solution was clear and transparent in light orange. The luminescent material solution is slowly introduced into the PMMA solution, and the solution is clear and transparent. Spin-coating (1200 rad/min), drying (60 ℃ C., 30 min) on a metal substrate such as a clean aluminum alloy, then placing the metal substrate into VOC for response, and testing fluorescence spectrum. As a result, it was found that the fluorescent sensor film, after being placed in an environment containing pyridine vapor, rapidly exhibited a phenomenon in which the maximum emission wavelength was blue-shifted (the new maximum emission wavelength was 527 nm), and the emission was changed from the original green to blue-green, and thus was useful as a sensor film for detecting pyridine VOCs; in addition, after the fluorescent sensing film is placed in an environment containing cyclohexylamine vapor, the fluorescent sensing film can quickly show a remarkable response effect of fluorescence quenching, and the fluorescent sensing film does not show obvious fluorescence response behaviors for various VOC vapors such as triethylamine, trimethylamine, ethanolamine, monomethylamine, 2-phenylpyridine, 3-phenylpyridine, diethylenetriamine, diisopropylamine, ammonia water and the like, so that the fluorescent sensing film can also be used as a selective fluorescent sensing film for detecting cyclohexylamine VOC. (see fig. 12, 13, 14, 15, 16).
Claims (6)
1. A binuclear cuprous cluster luminescent material compounded by nitrogen/phosphine ligands is characterized in that: the binuclear cuprous cluster luminescent material has a structural formula of (Xantphos) Cu 2I2(3-PhPy)2, wherein Xantphos is an electrically neutral diphosphine ligand 4, 5-bis (diphenylphosphine) -9, 9-dimethyl xanthene, and 3-PhPy is a nitrogen-containing ligand 3-phenylpyridine; the binuclear cuprous cluster luminescent material is in a triclinic system, the space group of P-1 is provided, and the unit cell parameters are as follows α＝86.946(2)°，β＝77.009(2)°，γ＝86.351(2)°，/>Z=2, d C＝1.533g/cm3, the crystalline colour of the material being yellow; the material structure is represented as a binuclear neutral complex, two cuprous ions adopt different tetrahedral coordination modes, and a double tetrahedral structure connected by sharing two bridge group iodide ions is formed; one cuprous in the structure adopts a CuI 2P2 tetrahedral coordination mode, wherein two I are bridge iodide ions, and two P come from a biphosphine ligand Xantphos; the other cuprous in the structure adopts a CuI 2N2 tetrahedral coordination mode, wherein two I are bridge iodide ions, and two N are respectively from two nitrogen-containing ligands 3-PhPy; and there is stronger supermolecular action between adjacent molecules, wherein one is that two biphosphine ligands in the adjacent molecules form stronger intermolecular pi.pi.stacking action through benzene rings through C-H.pi.interaction between benzene rings and xanthene ring components, and the other is that two 3-PhPy ligands in the adjacent molecules form stronger intermolecular pi.pi.pi.stacking action through benzene rings, and the structural rigidity of the interior of the material is improved; the molecular structure is shown as formula (I):
The binuclear cuprous cluster luminescent material is characterized in that the luminescent material is a broad spectrum excitation high-efficiency luminescent fluorescent powder, emits strong green fluorescence under the excitation of ultraviolet light and visible light within the wavelength range of 250 to 450 nanometers, has the maximum luminescent wavelength of 540nm and the color coordinate value of 0.3899,0.5280, and can be used as a photoluminescence green material or a luminescent layer green material in an electroluminescent device formed by multiple layers of organic materials.
2. The preparation method of the binuclear cuprous cluster light-emitting material according to claim 1, which comprises the following steps:
(1) Weighing CuI powder and powder of ligand Xantphos and 3-PhPy at room temperature, and adding into a ball milling tank;
(2) Adding ball grinding balls into a ball milling tank, wherein the ball-material ratio is 70:1, and then adding 2mL of acetonitrile;
(3) Putting the ball milling tank into a ball mill, setting the rotating speed of the ball mill to 160 revolutions per minute, and performing ball milling treatment for 4 hours;
(4) After ball milling, placing the ball milling tank in a vacuum oven for drying at 40 ℃, and obtaining crystalline powder which is a product;
(5) The molar ratio of the three reactants CuI to Xantphos is 3-PhPy and is 1:2:2, and the ball milling tank is an agate tank with the volume of 50 mL.
3. The fluorescence sensing application of a binuclear cuprous cluster luminescent material according to claim 1, wherein: after the luminescent material (Xantphos) Cu 2I2(3-PhPy)2 is placed in an environment containing pyridine vapor, the luminescent material can rapidly show the luminescent effect of color change and intensity change, and the maximum luminescent wavelength of the luminescent material is blue-shifted, so that the luminescent material can be used as a sensing material for detecting pyridine VOC.
4. The application of the fluorescent sensing film of the binuclear cuprous cluster luminescent material compounded by the nitrogen/phosphine ligand is characterized in that: the fluorescent sensing film is prepared by dissolving binuclear cuprous cluster luminescent material (Xantphos) Cu 2I2(3-PhPy)2 and then coating the dissolved Cu 2I2(3-PhPy)2 on test paper base paper, or dissolving and embedding the dissolved Cu 2I2(3-PhPy)2 in polymer solution and then coating a film on a substrate such as quartz; after the fluorescent sensing film is placed in an environment containing pyridine vapor, the fluorescent sensing film can rapidly show a luminous effect that the color is firstly reduced and then increased, the maximum luminous wavelength of the fluorescent sensing film is blue-shifted, and the new maximum luminous wavelength is 510nm, and the luminescence is changed from the original yellowish green to the bluish green, so that the fluorescent sensing film can be used as a sensing film for detecting pyridine VOC; in addition, after the fluorescent sensing film is placed in an environment containing cyclohexylamine vapor, the fluorescent sensing film can quickly show a remarkable response effect of fluorescence quenching, and the fluorescent sensing film does not show remarkable fluorescence response behaviors for monomethylamine, ethanolamine, diethanolamine, diisopropylamine, diethylenetriamine, trimethylamine, triethylamine, ammonia water, formaldehyde, 2-phenylpyridine and 3-phenylpyridine VOC vapor, so that the fluorescent sensing film can also be used as a selective fluorescent sensing film for detecting cyclohexylamine VOC; wherein the binuclear cuprous cluster luminescent material has a structural formula of (Xantphos) Cu 2I2(3-PhPy)2, xantphos in the formula is electrically neutral diphosphine ligand 4, 5-bis (diphenylphosphine) -9, 9-dimethyl xanthene, and 3-PhPy is nitrogen-containing ligand 3-phenylpyridine; the binuclear cuprous cluster luminescent material is in a triclinic system, the space group of P-1 is provided, and the unit cell parameters are as follows α＝86.946(2)°，β＝77.009(2)°，γ＝86.351(2)°，/>Z=2, d C＝1.533g/cm3, the crystalline colour of the material being yellow; the material structure is represented as a binuclear neutral complex, two cuprous ions adopt different tetrahedral coordination modes, and a double tetrahedral structure connected by sharing two bridge group iodide ions is formed; the molecular structure is shown as formula (I):
5. the use according to claim 4, wherein the preparation method of the paper-based fluorescence sensing film of the binuclear cuprous cluster luminescent material compounded by the nitrogen/phosphine-containing ligand comprises the following steps:
(1) Dissolving luminescent material (Xantphos) Cu 2I2(3-PhPy)2 powder in dichloromethane at room temperature;
(2) The cellulose film is manufactured into a shape which is required to be conveniently applied, and the shape is used as test paper base paper;
(3) Coating the luminescent material (Xantphos) Cu 2I2(3-PhPy)2 solution on test paper base paper at room temperature;
(4) And finally, drying the coated test paper under a vacuum condition, and obtaining the paper-based fluorescent sensing film after drying.
6. The use according to claim 4, wherein the preparation method of the polymer-based doped fluorescent sensing film of the binuclear cuprous cluster luminescent material compounded by the nitrogen/phosphine-containing ligand comprises the following steps:
(1) Dissolving PMMA solid in dichloromethane at room temperature;
(2) Dissolving luminescent material (Xantphos) Cu 2I2(3-PhPy)2 powder in dichloromethane at room temperature;
(3) Mixing the two solutions, and stirring to fully react to obtain a clear solution A;
(4) And spin-coating the clear solution A on a quartz plate, a metal substrate or a base such as test paper base paper at room temperature, and drying to obtain the doped fluorescent sensing film.
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