CN115043881B - Metal ion complex fluorescent probe, preparation thereof and application thereof in detecting chloroform gas molecules - Google Patents
Metal ion complex fluorescent probe, preparation thereof and application thereof in detecting chloroform gas molecules Download PDFInfo
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 71
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 56
- 238000004020 luminiscence type Methods 0.000 claims abstract description 24
- 238000005166 mechanoluminescence Methods 0.000 claims abstract description 20
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims abstract description 17
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- 238000005424 photoluminescence Methods 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- HHDPJRSXPOGIOP-UHFFFAOYSA-L manganese(2+);dibromide;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[Br-].[Br-] HHDPJRSXPOGIOP-UHFFFAOYSA-L 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- -1 methyl triphenylphosphine phosphine bromide Chemical compound 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
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- 239000003068 molecular probe Substances 0.000 description 5
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- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 4
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- 239000001116 FEMA 4028 Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic System
- C07F13/005—Compounds without a metal-carbon linkage
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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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
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
-
- 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 provides a metal ion complex fluorescent probe capable of detecting chloroform gas molecules and a preparation method thereof, wherein the molecular formula of the fluorescent probe is MnBr 4 (C 19 H 18 P) 2 Obtained by coordination reaction between methyltriphenylphosphine bromide and manganese bromide, the unit cell structure is composed of one [ MnBr ] 4 ] 2‑ Anionic center and two [ (C) 6 H 6 ) 3 P(CH 3 )] + The cationic ligand is monoclinic system and has excellent photoinduced and forced luminous performance. The fluorescent probe can diffuse chloroform molecules into a crystal structure and form C when encountering chloroform gas 39 H 37 Br 4 MnP 2 Cl 3 The structure becomes a trigonal system, and the luminescence property is quenched. High temperature promotes C 39 H 37 Br 4 MnP 2 Cl 3 The chloroform molecules in the complex are desorbed, and the luminous performance of the complex is effectively recovered. Therefore, the fluorescent probe not only can detect chloroform gas molecules in a simple and convenient mode of photoinduced luminescence and mechanoluminescence, but also has the characteristic of repeated use for a plurality of times.
Description
Technical Field
The invention relates to a metal ion complex fluorescent probe and a preparation method thereof, and simultaneously relates to application of the fluorescent probe in detecting chloroform gas molecules, belonging to the fields of advanced functional materials and intelligent sensing.
Background
Chloroform is a commonly used high-volatility organic raw material and solvent in industry, and can be used for producing freon (F-21, F-22, F-23) and the like, and can also be used as a solvent and extractant for antibiotics, spices, grease, resin, rubber and the like, so that the chloroform is extremely used in modern industry. Chloroform, however, is a highly toxic environmental contaminant that is potentially genotoxic, mutagenic and carcinogenic to humans and can cause fatal damage to the central nervous system, heart, liver and kidneys, and if exposed to air, can be oxidized to produce highly toxic phosgene. Therefore, the development of the sensor capable of detecting chloroform gas molecules in an air environment has great significance for effectively preventing chloroform from leaking and endangering human health.
In recent years, a fluorescent probe with characteristic luminescence in an ultraviolet-visible-near infrared region is capable of autonomously sensing and responding to changes of surrounding environment through changes of autofluorescence, and is greatly focused in the field of intelligent sensing and is in a rapidly developed state. For chloroform, ncube grafts azo dye modified beta-cyclodextrin molecules into a polymer, and the polymer is used as a molecular probe to detect chloroform, and when a host-guest compound is formed between the chloroform molecules and the beta-cyclodextrin, the microenvironment around a fluorescent group is changed, and fluorescence is quenched, namely the molecular probe can detect the chloroform molecules through fluorescence change (Physics and Chemistry of the Earth, 2014, 67-69:79-85.). However, the process of synthesizing the azo dye modified beta-cyclodextrin epichlorohydrin copolymer is relatively complex, and the probe can only detect chloroform molecules in a single fluorescence/quenching mode and cannot be reused, so that great difficulty exists in practical popularization and application.
Disclosure of Invention
The invention aims to provide a metal ion complex fluorescent probe and a preparation method thereof;
the invention further aims to provide an application of the fluorescent probe in detecting chloroform gas molecules, and the fluorescent probe can be used for better intelligent detection of toxic chloroform gas leaked in the environment.
The invention uses methyl triphenylphosphine bromide and manganese bromide tetrahydrate as raw materials to obtain MnBr with photoluminescence and mechanoluminescence performance through simple coordination reaction 4 (C 19 H 18 P) 2 Metal ion complex crystal whose unit cell consists of one [ MnBr ] 4 ] 2- Anionic center and two [ (C) 6 H 6 ) 3 P(CH 3 )] + The cationic ligand is monoclinic system. When the metal ion complex encounters chloroform gas, chloroform molecules can enter the crystal structure by diffusion, so that the unit cell of the chloroform molecules becomes a complex formed by two [ MnBr 4 ] 2- Four [ (C) 6 H 6 ) 3 P(CH 3 )] + And two CHCl 3 Co-composition, molecular formula change to C 39 H 37 Br 4 MnP 2 Cl 3 Belongs to a trigonal system, and both fluorescence and mechanoluminescence performance are quenched. More importantly, due to chloroform molecules and [ MnBr ] 4 ] 2- And [ (C) 6 H 6 ) 3 P(CH 3 )] + The combination between the chloroform and the organic solvent is an ionic dipole bond, the intermolecular acting force is weak, chloroform molecules can be desorbed through simple treatment at a high temperature of about 100 ℃ for 10-60 min, and the fluorescence and the forced luminescence efficiency of the complex can be quickly recovered. Therefore, the fluorescent probe provided by the invention can not only carry out intelligent detection on chloroform gas molecules in the environment in two simple modes of photoluminescence and mechanoluminescence, but also can be reused for a plurality of times, so that the application potential is huge.
1. MnBr 4 (C 19 H 18 P) 2 Preparation of metal ion complex crystal and luminous performance
The metal ion complex fluorescent probe is obtained by the coordination reaction between methyl triphenylphosphine bromide and manganese bromide, and the molecular formula is MnBr 4 (C 19 H 18 P) 2 The unit cell structure is composed of a [ MnBr ] 4 ] 2- Anionic center and two [ (C) 6 H 6 ) 3 P(CH 3 )] + The cationic ligand is monoclinic system,P2 1 space group has two properties of photoluminescence and forced luminescence.
The preparation method of the metal ion complex fluorescent probe comprises the steps of adding methyltriphenyl phosphine bromide and manganese bromide tetrahydrate into an organic solvent according to a molar ratio of 2:1, heating and refluxing for 1-12 hours at 40-80 ℃ in an inert atmosphere to fully carry out coordination reaction between methyltriphenyl phosphine bromide and manganese bromide, filtering, placing the obtained filtrate at room temperature, and crystallizing MnBr after the organic solvent is slowly volatilized 4 (C 19 H 18 P) 2 Metal ion complex crystals of (a).
Taking the metal ion complex crystal prepared in example 1 as an example, the crystal structure and luminescence properties thereof were examined using a single crystal diffractometer, a fluorescence spectrophotometer, an ultraviolet lamp, a camera, and the like. FIG. 1 is MnBr 4 (C 19 H 18 P) 2 The crystal structure diagram of the metal ion complex is not difficult to find: each unit cell contains one [ MnBr ] 4 ] 2- Anionic center and two [ (C) 6 H 6 ) 3 P(CH 3 )] + Cationic ligand, molar mass of material 929.19 g mol -1 The crystal structure is monoclinic system, which belongs toP2 1 Space group in which the unit cell parameters a, b and c axes are 9.7773 (12), 12.5160 (14) and 16.6131 (19) a, respectively, and the angles between the α, β and γ axes are 90 °, 105.096 (2) and 90 °, respectively, which indicates that the preparation of the molecular formula MnBr has been successful 4 (C 19 H 18 P) 2 Metal ion complex crystals of (a).
From the crystal structure diagram of FIG. 1, it can also be found that [ (C) 6 H 6 ) 3 P(CH 3 )] + The cationic ligands have not only C-H.pi.interactions (side-to-side) but also pi.pi.pi.interactions (dislocation face-to-face) so that the stacking configuration of the whole crystal is a dislocation parallel stacking mode. The interaction pi-face-to-face with respect to the C-H pi-side-to-face interaction not only promotes intermolecular transfer of carriers, but also is due to the effectThe complex crystal has good fluorescence and forced luminescence performances. FIG. 2 shows MnBr 4 (C 19 H 18 P) 2 The emission spectrum of the metal ion complex crystal shows that the light-emitting signal is strong, the peak position is near 515 nm, and the light-emitting color is Mn 2+ Green characteristic light of ions. Fig. 3 shows a photograph of a bright field of the complex crystal under ultraviolet light, which is seen to have very strong luminescence brightness. Fig. 3 also gives a photograph of a friction state in which it is sandwiched between two glass sheets, and it can be found that it also exhibits excellent mechanoluminescence. These data indicate that the synthetically prepared MnBr of the present invention 4 (C 19 H 18 P) 2 The metal ion complex crystal has good photoluminescence and mechanoluminescence performance.
2. MnBr 4 (C 19 H 18 P) 2 Intelligent detection and reusability of metal ion complex crystal to chloroform gas molecules
Handle MnBr 4 (C 19 H 18 P) 2 Placing the metal ion complex crystal in a closed container into which a small amount of chloroform solvent is poured, suspending, and checking the detection and identification performance of the complex crystal after the chloroform volatilizes to form steam. The results show that: the photoluminescent intensity of the complex crystal started to decrease significantly after 5h, the decrease in intensity was greater after 24 h and 48 h, and the luminescent signal was almost completely lost after 96 h, see fig. 2. Fig. 4 shows a photograph of the complex crystals under uv light and under dark field rubbing conditions, respectively, after various times of standing in chloroform vapor environment, it can be seen that most of the crystals had lost photoluminescent properties after 24 h, and the photoluminescent properties were quenched after 96 h. These crystals are rubbed by being sandwiched between two glass sheets, and the degree of decay in the mechanoluminescence performance is also similar to that of photoluminescence. However, if the complex crystal is placed in a vapor environment of acetone, butanone, n-hexane, methylene dichloride and other common organic solvents, the photoluminescence and mechanoluminescence properties of the complex crystal are not changed obviously, as shown in fig. 5. These data indicate that MnBr prepared according to the present invention 4 (C 19 H 18 P) 2 The metal ion complex crystal can carry out intelligent recognition detection on chloroform molecules in the environment through fluorescence and luminescent optical signal change caused by force.
To understand MnBr 4 (C 19 H 18 P) 2 The change in behavior of the metal ion complex in chloroform environment occurred by long-term standing was analyzed by a single crystal diffractometer for the crystal structure of the metal ion complex recrystallized in chloroform solvent, and as shown in FIG. 6, two [ MnBr ] were contained in each unit cell of the substance 4 ] 2- Four [ (C) 6 H 6 ) 3 P(CH 3 )] + And two CHCl 3 Co-composition, molecular formula change to C 39 H 37 Br 4 MnP 2 Cl 3 Molar mass of 1048.55 g mol -1 The crystal structure is changed into a trigonal system, belongs toP31c, wherein the unit cell parameters a, b and c have axis lengths of 10.852 (4), 10.852 (4) and 41.832 (14) a, respectively, and the angles between the α, β and γ axes are 90 °,90 ° and 120 °, respectively. These information indicate that chloroform molecules can diffuse into MnBr 4 (C 19 H 18 P) 2 In the unit cell of the metal ion complex, not only the crystal structure is obviously changed, but also the chloroform molecules with strong polarity are respectively connected with [ MnBr ] through ion dipole bonds 4 ] 2- Anionic centre [ (C) 6 H 6 ) 3 P(CH 3 )] + The cationic ligand acts to cause chloroform molecules to sandwich and the three to be in a linear arrangement. This structure disrupts pi.pi.face-to-face interactions in the original metal ion complex crystal and results in P in the ligand + And a light-emitting center Mn 2+ The distance between the two is increased from the original 6.2173A to 10.0538A, and the transfer process of carriers to the luminescence center is destroyed, so that the luminescence performance of the complex crystal is quenched.
Thus, chloroform molecules can diffuse into their crystal structure, changing their unit cell from two [ MnBr 4 ] 2- Four [ (C) 6 H 6 ) 3 P(CH 3 )] + And two pairs ofCHCl of each 3 Co-composition, molecular formula change to C 39 H 37 Br 4 MnP 2 Cl 3 The structure is changed into a trigonal system, so that the original MnBr can be obtained 4 (C 19 H 18 P) 2 The photoluminescence or/and the mechanoluminescence performance of the metal ion complex are quenched, so that the multifunctional intelligent detection of chloroform gas molecules is realized.
More importantly, the metal ion complex crystal placed in the chloroform environment for a long time is simply treated for 10-60 min in a high-temperature environment of 90-110 ℃, and the photoluminescence and mechanoluminescence performance can be effectively recovered, as shown in figure 7. Detection of C Using a synchronous thermal Analyzer (TG-DSC) 39 H 37 Br 4 MnP 2 Cl 3 The real-time change of the crystal along with the temperature rise can be found that: when the temperature was raised to around 100 ℃, the TG profile decreased significantly, indicating that there was desorption of material from the crystal. The decrease in the TG curve was about 9.48% in magnitude, while chloroform molecules were at C 39 H 37 Br 4 MnP 2 Cl 3 The theoretical mass ratio of the complex is about 11.38%, so that the desorption of substances at about 100 ℃ is well indicated as chloroform molecules. The chloroform molecules are desorbed mainly due to their association with [ MnBr ] 4 ] 2- And [ (C) 6 H 6 ) 3 P(CH 3 )] + The combination is weak ion dipole bond, and is easy to break under the condition of heating, thereby leading chloroform molecules to escape and leading the structure and the luminous performance of the complex to be restored to MnBr 4 (C 19 H 18 P) 2 The metal ion complex crystal is as it is. When it encounters chloroform vapors again, quenching occurs again, see FIG. 7. These data demonstrate that MnBr of the present invention 4 (C 19 H 18 P) 2 The fluorescent probe can be reused for detecting and identifying chloroform molecules.
Compared with the prior art, the invention has the following advantages:
the invention uses methyl triphenylphosphine bromide and manganese bromide tetrahydrate as raw materials to obtain the fluorescent and mechanoluminescence through simple coordination reactionMnBr 4 (C 19 H 18 P) 2 When the metal ion complex crystal encounters chloroform vapor molecules in the environment, the chloroform vapor molecules in the environment can enter a unit cell of the metal ion complex crystal through diffusion, and the luminous performance of the complex is quenched through changing the structure of the crystal, but the crystal structure and the luminous performance of the complex cannot be changed by other common organic solvent vapor molecules such as acetone, butanone, methylene dichloride, n-hexane and the like, so that the fluorescent probe can intelligently detect and identify chloroform gas molecules in the environment through photoluminescence and forced luminescence signals, and has more functions compared with the traditional azo dye modified beta-cyclodextrin molecular polymer molecular probe. More importantly, due to chloroform molecules and [ MnBr ] 4 ] 2- And [ (C) 6 H 6 ) 3 P(CH 3 )] + The combination between the two molecules is an ion dipole bond, the acting force is weaker, chloroform molecules can be desorbed through simple treatment at the high temperature of about 100 ℃ for 10-60 min, the luminous efficacy can be quickly recovered, and the luminous intensity and the quenching effect are almost unchanged after repeated for a plurality of times, so that the molecular probe also has good reusability, and therefore, the molecular probe has good application prospect in the field of intelligent detection of chloroform steam leakage.
Drawings
FIG. 1 is MnBr 4 (C 19 H 18 P) 2 The crystal structure and molecular structure of the metal ion complex.
FIG. 2 is MnBr 4 (C 19 H 18 P) 2 Emission spectra of the metal ion complexes after various times of exposure to chloroform vapors.
FIG. 3 is MnBr 4 (C 19 H 18 P) 2 Photograph of metal ion complex under bright field uv light and dark field rubbing conditions, respectively.
FIG. 4 is MnBr 4 (C 19 H 18 P) 2 Photographs of the metal ion complexes under uv and dark field rubbing conditions, respectively, after being placed in chloroform vapors for different times.
FIG. 5 is MnBr 4 (C 19 H 18 P) 2 Metal ionAnd (3) a luminescent photo of the sub-complex under the excitation of dark field ultraviolet light after the sub-complex is placed in other common organic solvent vapor for a long time.
FIG. 6 is C 39 H 37 Br 4 MnP 2 Cl 3 The crystal structure and molecular structure of the metal ion complex.
FIG. 7 is MnBr 4 (C 19 H 18 P) 2 Photoluminescence relative intensity and dark field triboluminescence photo of the metal ion complex subjected to chloroform vapor and heating treatment for multiple cycles.
Detailed Description
In order to make the technical scheme of the present invention better understood by those skilled in the art, the preparation and performance of the fluorescent probe capable of detecting chloroform gas molecules according to the present invention will be further described with reference to the following embodiments.
Example 1
(1) Analytically pure methyltriphenylphosphine bromide (C) was weighed separately using a balance in a molar ratio of 2:1 converted to mass percent (mol) 19 H 18 PBr) and manganese bromide tetrahydrate (MnBr) 2 ·4H 2 O) 1.25 g and 0.5 g each;
(2) Pouring the weighed raw materials of methyltriphenylphosphine bromide and manganese bromide tetrahydrate into an acetone solvent of 100 mL, and heating and refluxing for 6h at 60 ℃ in a nitrogen atmosphere to fully carry out coordination reaction between methyltriphenylphosphine bromide and manganese bromide;
(3) Filtering insoluble substances in the solution while the insoluble substances are hot, placing the obtained filtrate at room temperature for 48-h, and crystallizing MnBr after the acetone solvent is slowly volatilized 4 (C 19 H 18 P) 2 Metal ion complex crystals.
(4) The metal ion complex emits green fluorescence under ultraviolet light, and the metal ion complex is clamped between two glass sheets to emit green light by friction, so that the metal ion complex has good photoluminescence and mechanoluminescence performances.
(5) The metal ion complex is respectively placed in chloroform, acetone, butanone, normal hexane and dichloromethane vapor, only the fluorescence signal of the metal ion complex in the chloroform vapor is obviously weakened after 5 hours, the fluorescence and forced luminescence signal is basically disappeared after 96 h, and the fluorescence and forced luminescence performances of the metal ion complex in the acetone, butanone, normal hexane and dichloromethane vapor are basically unchanged, so that the metal ion complex has good intelligent detection effect on chloroform vapor molecules.
(6) And (3) putting the complex subjected to luminescence quenching in the step (5) into a blast oven, and heating at 100 ℃ for 30 min, wherein the complex not only recovers green fluorescence under ultraviolet light, but also can rapidly emit green characteristic light under friction conditions.
(7) Repeating the steps (5) and (6) for 2 times, wherein the photoluminescence and mechanoluminescence performances of the complex crystal are quenched after each time of encountering chloroform vapor, and the two luminescence capacities are recovered after each time of heating treatment, so that the complex crystal is a multifunctional and reusable fluorescent probe for detecting chloroform gas molecules.
Example 2
(1) Analytically pure methyltriphenylphosphine bromide (C) was weighed separately using a balance in a molar ratio of 2:1 converted to mass percent (mol) 19 H 18 PBr) and manganese bromide tetrahydrate (MnBr) 2 ·4H 2 O) 2.5 g and 1 g, respectively;
(2) Pouring the weighed raw materials of methyltriphenylphosphine bromide and manganese bromide tetrahydrate into 200 mL acetone, and heating and refluxing for 10 h at 58 ℃ in argon atmosphere to fully carry out coordination reaction between methyltriphenylphosphine bromide and manganese bromide;
(3) Filtering insoluble substances in the solution while the insoluble substances are hot, placing the obtained filtrate at room temperature for 96 h, and crystallizing MnBr after the acetone solvent is slowly volatilized 4 (C 19 H 18 P) 2 Metal ion complex crystals.
(4) The metal ion complex emits green fluorescence under ultraviolet light, and the metal ion complex is clamped between two glass sheets to emit green light by friction, so that the metal ion complex has good photoluminescence and mechanoluminescence performances.
(5) The metal ion complex is respectively placed in chloroform, acetone, butanone, normal hexane and dichloromethane vapor, only the fluorescence signal of the metal ion complex 4 h in the chloroform vapor is obviously weakened, the fluorescence and forced luminescence signal is basically disappeared after 88 h, and the fluorescence and forced luminescence performances of the metal ion complex in the acetone, butanone, normal hexane and dichloromethane vapor are basically unchanged, so that the metal ion complex has good intelligent detection effect on chloroform vapor molecules.
(6) And (3) putting the complex subjected to luminescence quenching in the step (5) into a blast oven, and heating at 100 ℃ for 45 min, wherein the complex not only recovers green fluorescence under ultraviolet light, but also can rapidly emit green characteristic light under friction conditions.
(7) Repeating the steps (5) and (6) for 3 times, wherein the photoluminescence and mechanoluminescence performances of the complex crystal are quenched after each time of encountering chloroform vapor, and the two luminescence capacities are recovered after each time of heating treatment, so that the complex crystal is a multifunctional and reusable fluorescent probe for detecting chloroform gas molecules.
Example 3
(1) Chemically pure methyltriphenylphosphine bromide (C) was weighed separately using a balance in terms of mass percent at a molar ratio of 2:1 19 H 18 PBr) and manganese bromide tetrahydrate (MnBr) 2 ·4H 2 O) 3.75 g g and 1.5g each;
(2) Pouring the weighed raw materials of methyltriphenylphosphine bromide and manganese bromide tetrahydrate into acetone of 300 mL, and heating and refluxing for 15 h at 60 ℃ in argon atmosphere to fully carry out coordination reaction between methyltriphenylphosphine bromide and manganese bromide;
(3) Filtering insoluble substances in the solution while the insoluble substances are hot, placing the obtained filtrate at room temperature for 150 h, and crystallizing MnBr after the acetone solvent is slowly volatilized 4 (C 19 H 18 P) 2 Metal ion complex crystals.
(4) The metal ion complex emits green fluorescence under ultraviolet light, and the metal ion complex is clamped between two glass sheets to emit green light by friction, so that the metal ion complex has good photoluminescence and mechanoluminescence performance.
(5) The metal ion complex is respectively placed in chloroform, acetone, butanone, normal hexane and dichloromethane vapor, only the fluorescence signal of the metal ion complex in the chloroform vapor is obviously weakened after 6 hours, the fluorescence and forced luminescence signal is basically disappeared after 90 h, and the fluorescence and forced luminescence performances of the metal ion complex in the acetone, butanone, normal hexane and dichloromethane vapor are basically unchanged, so that the metal ion complex has good intelligent detection effect on chloroform vapor molecules.
(6) And (3) putting the complex subjected to luminescence quenching in the step (5) into a blast oven, and heating at 105 ℃ for 25 min, wherein the complex not only recovers green fluorescence under ultraviolet light, but also can rapidly emit green characteristic light under friction conditions.
(7) Repeating the steps (5) and (6) for 4 times, wherein the photoluminescence and mechanoluminescence performances of the complex crystal are quenched after each time of encountering chloroform vapor, and the two luminescence capacities are recovered after each time of heating treatment, so that the complex crystal is a multifunctional and reusable fluorescent probe for detecting chloroform gas molecules.
Claims (7)
1. An application of a metal ion complex fluorescent probe in detecting chloroform gas molecules is characterized in that: the metal ion complex fluorescent probe is obtained by coordination reaction between methyl triphenylphosphine phosphine bromide and manganese bromide, and the molecular formula is MnBr 4 (C 19 H 18 P) 2 The unit cell structure is composed of a [ MnBr ] 4 ] 2- Anionic center and two [ (C) 6 H 6 ) 3 P(CH 3 )] + The cationic ligand is monoclinic system,P2 1 space group has two properties of photoluminescence and forced luminescence.
2. The use of a metal ion complex fluorescent probe according to claim 1 for detecting chloroform gas molecules, wherein: the preparation method of the metal ion complex fluorescent probe comprises the steps of adding methyl triphenylphosphine bromide and manganese bromide tetrahydrate into an organic solvent according to a molar ratio of 2:1, and carrying out inert atmosphereHeating and refluxing for 1-12 h at 40-80 ℃ to fully generate coordination reaction between methyl triphenylphosphine bromide and manganese bromide, filtering, standing the obtained filtrate at room temperature, and crystallizing MnBr after the organic solvent slowly volatilizes 4 (C 19 H 18 P) 2 Metal ion complex crystals of (a).
3. Use of a metal ion complex fluorescent probe according to claim 2 for detecting chloroform gas molecules, characterized in that: the organic solvent is any one of acetone, butanone and dichloromethane.
4. Use of a metal ion complex fluorescent probe according to claim 2 for detecting chloroform gas molecules, characterized in that: the inert atmosphere is nitrogen or argon.
5. Use of a metal ion complex fluorescent probe according to claim 2 for detecting chloroform gas molecules, characterized in that: the standing time at room temperature is 1-72 h.
6. The use of a metal ion complex fluorescent probe according to claim 1 for detecting chloroform gas molecules, wherein: mnBr is added to 4 (C 19 H 18 P) 2 The metal ion complex crystal is respectively placed in chloroform, acetone, butanone, methylene dichloride and n-hexane solvent steam, only chloroform molecules can lead MnBr 4 (C 19 H 18 P) 2 The photoluminescence and/or mechanoluminescence performance of the metal ion complex is quenched, so that the chloroform gas molecules are detected.
7. The use of a metal ion complex fluorescent probe according to claim 1 for detecting chloroform gas molecules, wherein: mnBr is added to 4 (C 19 H 18 P) 2 The metal ion complex crystal is placed in chloroform gas, photoluminescence or/and mechano-luminescence is quenched, and is heated for 10-60 min at the temperature of 90-110 ℃, photoluminescence or/and mechano-luminescence is carried outThe luminescence is recovered, and the repeated use of the fluorescent probe is realized.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924524A (en) * | 2012-10-29 | 2013-02-13 | 安徽大学 | Manganese complex two-photon absorption material with living cell development function and synthesis method thereof |
| CN104230996A (en) * | 2014-09-25 | 2014-12-24 | 天津师范大学 | Tetraphenyl ethylene manganese coordination compound, preparation method thereof, as well as application thereof as cadmium ion fluorescence probe |
| CN105924449A (en) * | 2016-04-22 | 2016-09-07 | 东华大学 | Preparation and application for reaction type fluorescein fluorescent probe capable of detecting mercury ions |
| CN106654300A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Method for preparing monodisperse metal atom/graphene composite material employing electrochemical dissolved graphite |
| CN107602449A (en) * | 2017-09-12 | 2018-01-19 | 常州工程职业技术学院 | A kind of preparation and application of the Zn complex fluorescence probe with graphite-like structure |
| CN109054036A (en) * | 2018-07-16 | 2018-12-21 | 重庆师范大学 | Sandwich type manganese coordination polymer, preparation method and its application in cation detection of blue-green fluorescent |
| CN110000395A (en) * | 2019-04-16 | 2019-07-12 | 天津师范大学 | The method and its application of one-step synthesis method fluorescence metal manganese nano-cluster |
| JP2020041981A (en) * | 2018-09-13 | 2020-03-19 | 株式会社東芝 | Organic substance probe and molecule detector |
| AU2020103559A4 (en) * | 2020-01-13 | 2021-02-04 | Qilu University Of Technology | Ratiometric fluorescent probe for detecting hypochlorous acid, and preparation method and use thereof |
| KR20210095475A (en) * | 2020-01-23 | 2021-08-02 | 경희대학교 산학협력단 | Fluorescent probe compound for the detection of malononitrile and use thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117282B (en) * | 2019-05-13 | 2020-07-10 | 五邑大学 | Zinc ion fluorescent probe compound and preparation method and application thereof |
-
2022
- 2022-07-04 CN CN202210778016.XA patent/CN115043881B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924524A (en) * | 2012-10-29 | 2013-02-13 | 安徽大学 | Manganese complex two-photon absorption material with living cell development function and synthesis method thereof |
| CN104230996A (en) * | 2014-09-25 | 2014-12-24 | 天津师范大学 | Tetraphenyl ethylene manganese coordination compound, preparation method thereof, as well as application thereof as cadmium ion fluorescence probe |
| CN105924449A (en) * | 2016-04-22 | 2016-09-07 | 东华大学 | Preparation and application for reaction type fluorescein fluorescent probe capable of detecting mercury ions |
| CN106654300A (en) * | 2016-12-19 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Method for preparing monodisperse metal atom/graphene composite material employing electrochemical dissolved graphite |
| CN107602449A (en) * | 2017-09-12 | 2018-01-19 | 常州工程职业技术学院 | A kind of preparation and application of the Zn complex fluorescence probe with graphite-like structure |
| CN109054036A (en) * | 2018-07-16 | 2018-12-21 | 重庆师范大学 | Sandwich type manganese coordination polymer, preparation method and its application in cation detection of blue-green fluorescent |
| JP2020041981A (en) * | 2018-09-13 | 2020-03-19 | 株式会社東芝 | Organic substance probe and molecule detector |
| CN110000395A (en) * | 2019-04-16 | 2019-07-12 | 天津师范大学 | The method and its application of one-step synthesis method fluorescence metal manganese nano-cluster |
| AU2020103559A4 (en) * | 2020-01-13 | 2021-02-04 | Qilu University Of Technology | Ratiometric fluorescent probe for detecting hypochlorous acid, and preparation method and use thereof |
| KR20210095475A (en) * | 2020-01-23 | 2021-08-02 | 경희대학교 산학협력단 | Fluorescent probe compound for the detection of malononitrile and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| Characterization, phase change and conductivity crossover of new luminescent ferroelectric Mn (II) organic-inorganic hybrid;Mohga F. Mostafa等，;《Materials Chemistry and Physics》 * |
| Triboluminescence and Vapor-Induced Phase Transitions in the Solids of Methyltriphenylphosphonium Tetrahalomanganate(II) Complexes;Sujitha Balsamy等，;《Inorg. Chem.》;第6054−6059页 * |
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