CN111471455B - Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material - Google Patents
Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material Download PDFInfo
- Publication number
- CN111471455B CN111471455B CN202010418464.XA CN202010418464A CN111471455B CN 111471455 B CN111471455 B CN 111471455B CN 202010418464 A CN202010418464 A CN 202010418464A CN 111471455 B CN111471455 B CN 111471455B
- Authority
- CN
- China
- Prior art keywords
- viologen
- acetophenone
- substituted
- thiazolo
- thiazolyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 18
- 125000000335 thiazolyl group Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 4
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 150000008062 acetophenones Chemical class 0.000 claims abstract description 4
- 239000000090 biomarker Substances 0.000 claims abstract description 4
- 239000012769 display material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- -1 sodium tetraphenylborate Chemical compound 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KBXDZYVLDKNMQL-UHFFFAOYSA-N 2,5-dipyridin-4-yl-[1,3]thiazolo[5,4-d][1,3]thiazole Chemical compound C1=NC=CC(C=2SC=3N=C(SC=3N=2)C=2C=CN=CC=2)=C1 KBXDZYVLDKNMQL-UHFFFAOYSA-N 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- 238000011161 development Methods 0.000 abstract description 11
- 230000005284 excitation Effects 0.000 abstract description 9
- 238000005424 photoluminescence Methods 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 abstract 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NCYCYZXNIZJOKI-IOUUIBBYSA-N 11-cis-retinal Chemical class O=C/C=C(\C)/C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-IOUUIBBYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 102000004330 Rhodopsin Human genes 0.000 description 1
- 108090000820 Rhodopsin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The structural formula of the acetophenone and derivative substituted thiazolyl viologen strong fluorescence color-changing material is shown as the following formula, and the synthesis method comprises the following steps: reacting 2, 5-di (4-pyridyl) thiazolo [5,4-d ]]Mixing thiazole, alpha-halogenated acetophenone or substituted derivatives thereof in a solvent, and heating and refluxing to obtain the target product. The 4PV & 2Br viologen of the invention has high distinguished solvent color development, emits 467nm bright blue fluorescence under the excitation of light with the maximum excitation wavelength of 397nm, has quantum yield as high as 0.97, has fluorescence life as long as 1.93ns, and has stable excitation state; the aqueous solution and the prepared PVA flexible transparent luminescent film can still keep stable blue light emission after being placed for a long time, can also keep stable luminescent performance in the aqueous solution with the pH value of 3-7, can keep stable emission under long-term ultraviolet illumination, and can be developed into novel biological markers and luminescent display materials. 4 PV.2B (Ph) 4 The viologen not only has good photoluminescence performance but also has excellent photochromic performance, and can be developed into a novel photochromic material.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method and application of a thiazolyl viologen fluorescent photochromic material substituted by acetophenone and derivatives thereof.
Background
The traditional viologen compound is 1,1 '-disubstituted-4, 4' -bipyridine cation salt, is widely researched due to simple synthesis and capability of generating two-step reversible redox reaction accompanied with obvious color change under abundant external stimuli (such as light, heat, electricity and pressure), and is mainly applied to the fields of light, heat, electrochromic devices, molecular recognition and the like.
As an electron-deficient organic chromogenic material, the viologen compound can generate free radicals through electron transfer with electron donors to develop color, but the free radicals are easily quenched by oxygen in the air or dissolved oxygen in solution, so that the color development cannot be lasting and the reversibility is lost, the viologen compound can only be used under the anaerobic condition, and the potential application value and the prospect of the viologen compound material are seriously limited. Modification of substituents on the 4,4' -bipyridine backbone and branches by molecular design is the best approach to solve this problem. Researchers find that by designing and expanding viologen molecules to have a larger conjugate plane and more excellent electron accepting capability, a more sensitive response and a more stable cation free radical color development state are achieved. At present, research based on the expansion of viologen performance is expanded to emerging fields such as organic batteries, photolysis water catalysts, biological imaging and the like except in the field of color-changing materials.
On the basis of reasonable molecular design, the introduction of the large conjugated chromophoric group can better stabilize free radicals to further improve the color development sensitivity, and is an effective way for regulating and controlling the luminous performance of the viologen compound. At present, few rhodopsin compounds with strong luminescence are available, a few reports mainly focus on the composition of the rhodopsin and materials such as supramolecules and MOFs, and the composition has poor water solubility, low quantum yield and limited application value. The research for designing and synthesizing the color-changing sensitive and strong-luminescence viologen compound is not reported at present.
Disclosure of Invention
The invention aims to maintain and stabilize the color-changing performance of the viologen, realize the light-emitting regulation and control of the viologen in the solution, expand and realize the development of multifunctional materials of viologen compounds by introducing the extended fluorescent chromophore.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides an acetophenone and derivative substituted thiazolyl viologen strong fluorescent material, the structural formula is shown as the following formula:
wherein R is 1 、R 2 H, F, cl, br, OH, COOH or phenyl; x is Cl, br or tetraphenylboron.
The second aspect of the invention also provides a preparation method of the acetophenone and derivative substituted thiazolyl viologen strong fluorescent material, which is one of the following methods:
the method comprises the following steps: mixing 2, 5-di (4-pyridyl) thiazolo [5,4-d ] thiazole, alpha-halogenated acetophenone or substituted derivatives thereof in a solvent to obtain a mixed solution; refluxing the mixed solution under heating for a period of time, cooling, collecting precipitate, washing, and drying to obtain yellow powder, i.e. the thiazolo [5,4-d ] thiazolyl viologen substituted by acetophenone and its derivatives;
the second method comprises the following steps: dissolving the acetophenone and derivative substituted thiazolo [5,4-d ] thiazolyl viologen prepared by the first method in a solvent, adding sodium tetraphenylborate, stirring for a period of time under the conditions of sealing and keeping out of the sun, collecting the precipitate, washing and drying to obtain yellow powder, namely the acetophenone substituted thiazolo [5,4-d ] thiazolyl bis-tetraphenylboron viologen.
Preferably, the molar ratio of the 2, 5-bis (4-pyridyl) thiazolo [5,4-d ] thiazole to the alpha-haloacetophenone or substituted derivative in the first method is 1.
Preferably, the solvent in the first method is anhydrous acetonitrile, anhydrous N, N-dimethylformamide or a mixture of anhydrous acetonitrile and anhydrous N, N-dimethylformamide in a volume ratio of 1.
Preferably, in the first method, the heating condition is 80-130 ℃, and the reflux time is 3-24 h.
Preferably, in the first method, the cooling, collecting the precipitate, washing and drying specifically include: cooling to room temperature, centrifuging to obtain precipitate, washing with anhydrous acetonitrile or anhydrous DMF and acetone, washing until the washing liquid is colorless, and drying at 80 deg.c in vacuum for 8-12 hr.
Preferably, in the second method, the mass ratio of the acetophenone and derivative thereof substituted thiazolo [5,4-d ] thiazolyl viologen to the sodium tetraphenylborate is 4.
Preferably, the solvent in the second method is a mixed solution of acetonitrile and ultrapure water in a volume ratio of 1.
Preferably, in the second method, the washing and drying specifically include: washing the product with ethanol and ultrapure water for multiple times, centrifuging, and drying the product at 100 ℃ for 8h under vacuum.
As a third aspect, the invention also provides the application of the acetophenone and derivative substituted thiazolyl viologen strong fluorescent material as a biomarker and/or luminescent display material.
Compared with the prior art, the invention has the following beneficial effects:
the synthetic method has the advantages of simple process, low synthetic cost, high yield of 85-96 percent, high utilization rate of raw materials and suitability for large-scale production;
the 4PV & 2Br viologen of the invention has high distinguished solvent color development and has application potential in the aspect of solvent color development; the 4PV & 2Br viologen emits 467nm bright blue fluorescence under the excitation of light with the maximum excitation wavelength of 397nm, the quantum yield is as high as 0.97, the fluorescence lifetime is 1.93ns, and the viologen has a stable excitation state; the aqueous solution and the prepared PVA flexible transparent luminescent film can be placed for a long time under the laboratory condition, stable blue light emission can be still kept after the film is placed for more than one year under the air atmosphere, the luminescent performance can be kept stable in the aqueous solution with the pH value of 3-7, the emission can be kept stable under long-term ultraviolet illumination, and the film can be developed into novel biological markers and luminescent display materials;
4PV·2B(Ph) 4 the viologen not only has good photoluminescence performance but also has excellent photochromic performance, and can be developed into a novel photochromic material.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of viologen prepared in examples 1 and 2 of the present invention;
FIG. 2 shows the NMR spectrum of viologen prepared in example 3 of the present invention;
FIG. 3 is a NMR spectrum of viologen prepared in example 4 of the present invention;
FIG. 4 is a solvent color effect of 4 PV.2Br viologen in MeOH, etOH, DMF, DMA, meCN, and NMP (left to right) in example 5 of the invention;
FIG. 5 is the UV-VIS absorption spectra of 4 PV.2Br viologen in example 5 of the present invention in different solvents and at different concentrations;
FIG. 6 is an absorption and emission spectrum of an aqueous 4 PV.2 Br viologen solution in example 6 of the present invention (inset: fluorescence lifetime decay curve);
FIG. 7 shows fluorescence emission spectra (a) of 4 PV.2Br viologen in water solution at different pH values (1-10) and emission of 467nm fluorescence emission peak at different pH values (b) in example 6 of the present invention;
FIG. 8 is a fluorescence emission spectrum of an aqueous 4 PV.2Br viologen solution in example 6 of the present invention before and after two hours of light irradiation;
FIG. 9 shows the concentration of 1X 10 under natural light and under a 365nm ultraviolet lamp in example 7 of the present invention -4 The display effect of the fluorescent test paper (a) written by the 4PV & 2Br viologen aqueous solution of M and the PVA flexible luminescent film (b) based on the 4PV & 2Br viologen are compared;
FIG. 10 shows 4 PV.2B (Ph) in example 8 of the present invention 4 A photoluminescent and photochromic picture written in a viologen acetone solution;
FIG. 11 shows 4 PV.2B (Ph) in example 8 of the present invention 4 Changing color of the viologen powder under the irradiation of 365nm ultraviolet lamps for different time;
FIG. 12 shows 4 PV.2B (Ph) in example 8 of the present invention 4 Ultraviolet-visible spectrum of solid material with viologen under 365nm ultraviolet lamp.
The specific implementation mode is as follows:
example 1
The synthesis method of acetophenone substituted thiazolo [5,4-d ] thiazolyl dibromo viologen (4 PV & 2 Br) comprises the following steps:
1.35mmol (0.4 g) of 2, 5-bis (4-pyridyl) thiazolo [5,4-d ] thiazole (Ptz) and 4.52mmol (0.9 g) of 2-bromoacetophenone were weighed into a flask, and the above solid-liquid mixture was reacted under reflux at 100 ℃ for 6 hours with 8ml of anhydrous acetonitrile as a solvent. Yellow precipitate is separated out in the reaction process, the mixture is cooled to room temperature after the reaction is finished, the mixture is centrifuged and washed for a plurality of times by anhydrous acetonitrile and acetone respectively until the washing liquid is changed from light yellow to colorless, the precipitate is dried for 8 hours under the vacuum condition of 80 ℃, and 0.91g of bright yellow powder is collected. The yield of acetophenone-substituted thiazolo [5,4-d ] thiazolyldibromoviologen calculated based on the starting material Ptz was 96%.
Physical parameters of the compound are as follows:
the molecular formula is as follows: c 30 H 22 N 4 O 2 S 2 Br 2
Structural formula (la):
chinese naming: acetophenone disubstituted thiazolo [5,4-d ] thiazolyl dibromo viologen
Molecular weight: 694.45
Appearance: bright yellow powder
Hydrogen nuclear magnetic resonance (FIG. 1) 1 H NMR(400MHz,DMSO,25℃):δ9.15(d,J＝7.15Hz,4H),8.93(d,J＝7.05Hz,4H),8.10(d,J＝7.25Hz,4H),7.83(t,J＝8.09Hz,2H),7.70(t,J＝7.64Hz,4H),6.52(s,4H).
Example 2
The method for synthesizing acetophenone substituted thiazolo [5,4-d ] thiazolyl dibromo viologen in the embodiment is as follows:
0.34mmol (0.1 g) of 2, 5-bis (4-pyridyl) thiazolo [5,4-d ] thiazole (Ptz) and 0.80mmol (0.165 g) of 2-bromoacetophenone were weighed into a flask, and the above solid-liquid mixture was refluxed at 120 ℃ for 6 hours with 5ml of anhydrous DMF as a solvent. Yellow precipitate is separated out in the reaction process, the mixture is cooled to room temperature after the reaction is finished, the mixture is centrifuged and washed for a plurality of times by using anhydrous DMF and acetone respectively until the washing liquid is changed from brown yellow to colorless, the precipitate is dried for 8 hours at 80 ℃ in vacuum, and 0.20g of bright yellow powder is collected. The acetophenone-substituted thiazolo [5,4-d ] thiazolyl viologen yield, calculated on the basis of the starting material Ptz, was 86%. The resulting compound was the same as in example 1.
Example 3
The synthesis method of acetophenone substituted thiazolo [5,4-d ] thiazolyl dichloro viologen (4 PV & 2 Cl):
0.34mmol (0.10 g) of 2, 5-bis (4-pyridyl) thiazolo [5,4-d ] thiazole (Ptz) and 1.0mmol (0.155 g) of 2-chloroacetophenone were weighed in a flask, and the above solid-liquid mixture was refluxed at 120 ℃ for 24 hours with 4ml of anhydrous acetonitrile and anhydrous DMF at a volume ratio of 1. Yellow precipitate is separated out in the reaction process, the mixture is cooled to room temperature after the reaction is finished, the mixture is centrifuged and washed for multiple times by using anhydrous DMF and acetone respectively until the washing liquid is changed from brown yellow to colorless, the precipitate is dried for 8 hours at 80 ℃ in vacuum, and 0.179g of bright yellow powder is collected. The acetophenone-substituted thiazolo [5,4-d ] thiazolyl viologen yield, calculated on the basis of the starting material Ptz, was 87%.
Physical parameters of the compound are as follows:
the molecular formula is as follows: c 30 H 22 N 4 O 2 S 2 Cl 2
Structural formula (xvi):
chinese naming: acetophenone disubstituted thiazolo [5,4-d ] thiazolyl dichloro viologen
Molecular weight: 605.55
Appearance: yellow powder
Hydrogen nuclear magnetic resonance (FIG. 2) 1 H NMR(600MHz,D 2 O,25℃):δ8.92(d,J＝6.00Hz,4H),8.69(d,J＝6.00Hz,4H),8.01(d,J＝7.80Hz,4H),7.74(t,J＝7.80Hz,2H),7.57(t,J＝8.70Hz,4H),6.46(s,4H).
Example 4
Acetophenone substituted thiazolo [5,4-d ]]Thiazolyl bis tetraphenyl boron viologen (4 PV.2B (Ph) 4 ) Method for synthesizing (2)
0.4g of 4 PV.2B (Ph) prepared in example one was weighed out 4 The viologen was dissolved in 50ml of acetonitrile/ultrapure water solution at a volume ratio of 1:1, 0.5g (1.46 mmol) of sodium tetraphenylborate was weighed and poured into a beaker, a large amount of orange-yellow precipitate was generated instantaneously during the reaction, the beaker was sealed with a sealing film, and stirred with a stirrer in a dark environment for 2 hours. The precipitate was washed several times with ethanol and ultrapure water and, after centrifugation, the product was dried under vacuum at 100 ℃ for 8h to give 0.63g of a yellow powder with a yield of 93% calculated on the basis of 4PV · 2 Br.
Physical parameters of the compound are as follows:
the molecular formula is as follows: c 78 H 62 B 2 N 4 O 2 S 2
Structural formula (xvi):
chinese naming: acetophenone disubstituted thiazolo [5,4-d ] thiazolyl bis tetraphenylboron viologen
Molecular weight: 1173.05
Appearance: yellow powder
Hydrogen nuclear magnetic resonance spectrum (FIG. 3) (400MHz, d 6- DMSO,25℃)：δ9.11(d,J＝6.80Hz,4H),8.91(d,J＝7.20Hz,4H),8.09(d,J＝7.20Hz,4H),7.82(t,J＝8.00Hz,2H),7.69(t,J＝7.80Hz,4H),7.17(s,4H),6.92(t,J＝7.40Hz,4H),6.78(t,J＝7.20Hz,4H),6.50(s,4H).
Example 5
As shown in fig. 4, the viologen compound (4 PV · 2 Br) prepared in the first example was dissolved in different solvents, and at a certain concentration, the viologen had a significant solvent color development effect, and the color development time was maintained for 2 hours. Measured by UV-visible absorption spectroscopy (FIG. 5, solvents MeOH, etOH, DMF, DMA, meCN, and NMP, respectively; concentration range 1.0 x 10 -4 M to 5.0 x 10 -7 M) with different solvent-chromogenic absorption maxima: methanol (565 nm), ethanol (583 nm), acetonitrile (610 nm), N-dimethylformamide (610 nm), N-Dimethylacetamide (606 nm) and N-methylpyrrolidone (648 nm). The viologen compound has high-resolution solvent color development and can be applied as a solvent color development material.
Example 6
As shown in FIG. 6, 4 PV.2 Br viologen prepared in example 1 was prepared as a 0.1mmol aqueous solution in ultrapure water, and it was determined that the viologen aqueous solution had 467nm blue emission, a fluorescence quantum yield of 0.97, and a fluorescence lifetime of 1.93ns under excitation at a wavelength of 397nm as a maximum excitation wavelength. The 4 pv.2br viologen was shown to have a stable excited state.
The 4PV · 2Br viologens prepared in example 1 were prepared as 0.01mmol aqueous solutions having pH 1 to 10, respectively, and their emission spectra excited at a maximum excitation wavelength of 397nm were measured (fig. 7).
The 4PV & 2Br viologen prepared in example 1 was prepared into 0.01mmol aqueous solution, and the emission spectrum thereof before (black) and after (red) ultraviolet irradiation at 2h 365nm was measured (FIG. 8).
As can be seen from FIGS. 7 and 8, the 4PV & 2Br viologen can keep stable luminescence property in aqueous solution with pH value of 3-7 and stable emission under long-term ultraviolet illumination, and shows the application potential in the aspects of biological marking and luminescence display.
Example 7
The 4PV & 2Br viologen prepared in the first example is prepared into 20ml of 0.1mmol aqueous solution, 10wt% of polyvinyl alcohol (PVA) and 5wt% of glycerol are added, the mixture is heated and stirred for 4-6h at the temperature of 60-80 ℃ to be dissolved, a film is prepared by adopting a spin coating method or a pulling method, and the PVA flexible luminescent film emits bright blue fluorescence under ultraviolet light (figure 9 b). FIG. 9a shows 4 PV.2Br is arranged at a concentration of 1X 10 -4 M aqueous solution is written to obtain a picture of the display effect of the fluorescent test paper under natural light and under 365nm ultraviolet lamp irradiation respectively. The 4 pv.2br viologen maintains stable blue emission even when left in air for a long time.
Example 8
FIG. 10 shows 4 PV.2B (Ph) prepared in example four 4 The concentration of the viologen is 1 multiplied by 10 -4 Photoluminescence and photochromic photographs of test strips written in acetone solution of M.
As shown in FIG. 11, 4 PV.2B (Ph) 4 The viologen can be obviously discolored after being irradiated by a 365nm ultraviolet lamp for 10s, can be kept unchangeable in natural light, can be discolored about one week under the dark condition, can be discolored after being heated for 2 hours at 120 ℃, and has reversibility. FIG. 12 shows 4PV 2B (Ph) 4 Ultraviolet-visible spectrum of solid material with viologen under 365nm ultraviolet lamp.
As can be seen from FIGS. 10-12, 4PV 2B (Ph) 4 The viologen not only has good photoluminescence performance, but also has excellent photochromic performance, and has the potential of being developed into a novel photochromic material.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: the embodiments can be changed, modified, replaced and modified without departing from the principle and the spirit of the invention, for example, 2-bromoacetophenone and 2-chloroacetophenone can be replaced by various acetophenone derivatives containing F, br, cl, OH, COOH or phenyl, etc., and the changes, modification and replacement can obtain equivalent effects and also belong to the protection scope of the invention.
Claims (10)
1. The acetophenone and derivative substituted thiazolyl viologen fluorescent material is characterized in that the structural formula is shown as the following formula:
i.
wherein R is 1 、R 2 H, F, cl, br, OH, COOH or phenyl; x is Cl, br or tetraphenylboron.
2. Use of acetophenone and its derivatives substituted thiazolyl viologen fluorescent material according to claim 1 as biomarker and/or luminescent display material.
3. The method for preparing the acetophenone and its derivative substituted thiazolyl viologen fluorescent material in the claim 1 is characterized in that it is one of the following methods:
the method comprises the following steps: mixing 2, 5-di (4-pyridyl) thiazolo [5,4-d ] thiazole, alpha-halogenated acetophenone or substituted derivatives thereof in a solvent to obtain a mixed solution; refluxing the mixed solution under heating for a period of time, cooling, collecting precipitate, washing, and drying to obtain yellow powder, namely, the thiazolo [5,4-d ] thiazolyl dibromo viologen substituted by acetophenone and derivatives thereof;
the second method comprises the following steps: dissolving the acetophenone and derivative substituted thiazolo [5,4-d ] thiazolyl dibromo viologen prepared by the first method in a solvent, adding sodium tetraphenylborate, stirring for a period of time under the conditions of sealing and keeping out of the sun, collecting the precipitate, washing and drying to obtain yellow powder, namely the acetophenone substituted thiazolo [5,4-d ] thiazolyl bis tetraphenylboron viologen.
4. The method as claimed in claim 3, wherein the molar ratio of the 2, 5-bis (4-pyridyl) thiazolo [5,4-d ] thiazole to the α -haloacetophenone or substituted derivative in the first method is 1.
5. The method according to claim 3, wherein the solvent in the first method is anhydrous acetonitrile, anhydrous N, N-dimethylformamide or a mixture of anhydrous acetonitrile and anhydrous N, N-dimethylformamide in a volume ratio of 1.
6. The method according to claim 3, wherein in the first method, the heating condition is 80-130 ℃ and the reflux time is 3-24 h.
7. The method according to claim 3, wherein in the first method, the cooling, the collecting of the precipitate, the washing and the drying specifically comprise: cooling to room temperature, centrifuging to obtain precipitate, washing with anhydrous acetonitrile or anhydrous DMF, acetone, washing to colorless, and vacuum drying at 80 deg.c for 8-12 hr.
8. The method as claimed in claim 3, wherein in the second method, the mass ratio of the acetophenone and the derivative thereof substituted thiazolo [5,4-d ] thiazolyldibromoviologen to the sodium tetraphenylborate is 4.
9. The method according to claim 3, wherein the solvent in the second method is a mixture of acetonitrile and ultrapure water in a volume ratio of 1.
10. The method according to claim 3, wherein in the second method, the washing and drying specifically comprise: washing the product with ethanol and ultrapure water for multiple times, centrifuging, and drying the product at 100 ℃ for 8h under vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010418464.XA CN111471455B (en) | 2020-05-18 | 2020-05-18 | Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010418464.XA CN111471455B (en) | 2020-05-18 | 2020-05-18 | Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111471455A CN111471455A (en) | 2020-07-31 |
| CN111471455B true CN111471455B (en) | 2022-10-11 |
Family
ID=71762363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010418464.XA Active CN111471455B (en) | 2020-05-18 | 2020-05-18 | Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111471455B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894524A (en) * | 2022-12-07 | 2023-04-04 | 上海大学 | Preparation of acetophenone substituted thiazolyl viologen metal halide color-changing fluorescent material and application of anti-counterfeiting ink |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860875A (en) * | 2015-05-14 | 2015-08-26 | 上海大学 | Substituent acetophenone group purpurine derivative of high-sensitivity color changing material and synthetic method thereof |
| CN106432061A (en) * | 2016-06-12 | 2017-02-22 | 上海大学 | High sensitivity color-changing acetophenone substituent viologen compound and synthesis method thereof |
| CN108373444A (en) * | 2018-03-09 | 2018-08-07 | 上海大学 | Fluorescence viologen derivative and its application and preparation method |
| CN109096311A (en) * | 2018-07-24 | 2018-12-28 | 郑州大学 | It is a kind of to detect the fluorescence probe of water, preparation method and applications |
-
2020
- 2020-05-18 CN CN202010418464.XA patent/CN111471455B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860875A (en) * | 2015-05-14 | 2015-08-26 | 上海大学 | Substituent acetophenone group purpurine derivative of high-sensitivity color changing material and synthetic method thereof |
| CN106432061A (en) * | 2016-06-12 | 2017-02-22 | 上海大学 | High sensitivity color-changing acetophenone substituent viologen compound and synthesis method thereof |
| CN108373444A (en) * | 2018-03-09 | 2018-08-07 | 上海大学 | Fluorescence viologen derivative and its application and preparation method |
| CN109096311A (en) * | 2018-07-24 | 2018-12-28 | 郑州大学 | It is a kind of to detect the fluorescence probe of water, preparation method and applications |
Non-Patent Citations (3)
| Title |
|---|
| A π-Conjugation Extended Viologen as a Two-Electron Storage Anolyte for Total Organic Aqueous Redox Flow Batteries;Jian Luo 等;《Angew. Chem. Int. Ed.》;20171213;第57卷;231-235 * |
| High Sensitivity Viologen for a Facile and Versatile Sensor of Base and Solvent Polarity in Solution and Solid State in Air Atmosphere;Wei Shi 等;《ACS Appl. Mater. Interfaces》;20150611;第7卷;14493-14500 * |
| 紫精化合物的合成与应用研究进展;韩香草 等;《合成化学》;20190619;第27卷;576-583 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111471455A (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109400899B (en) | Lead coordination polymer and preparation method and application thereof | |
| CN107573928B (en) | A kind of solid-state up-conversion luminescent material and preparation method thereof based on T-T annihilation | |
| Zhao et al. | Mechanofluorochromism of difluoroboron β-ketoiminate boron complexes functionalized with benzoxazole and benzothiazole | |
| Li et al. | A reversible vapor-responsive fluorochromic molecular platform based on coupled AIE–ESIPT mechanisms and its applications in anti-counterfeiting measures | |
| CN102899029B (en) | Luminescent material of cuprous iodide complex and preparation method thereof | |
| CN110461820B (en) | Organic luminophores | |
| CN112679518B (en) | Pure organic room temperature phosphorescent material based on thiochromanone derivative and preparation method and application thereof | |
| CN112010806B (en) | Stimulus-response type organic long-afterglow material and preparation method and application thereof | |
| CN108947766B (en) | Fluorine-containing tetraphenylethylene compound and preparation method and application thereof | |
| CN111440193B (en) | Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof | |
| WO2023071855A1 (en) | Hydrazone-based zn (ii) coordination complex photochromic material, preparation and use thereof | |
| Zhou et al. | D–A type luminophores with a twisted molecular conformation constructed by phenoxazine and diphenylsulfone showing high contrast mechanofluorochromism | |
| CN111471455B (en) | Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material | |
| CN106279214B (en) | A kind of photic and difunctional iodine silver hydrochlorate off-color material of thermic and preparation method thereof | |
| CN107759504B (en) | Dual-phase organic fluorescent material with strong fluorescence in solid and liquid states and preparation method thereof | |
| Xu et al. | Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline | |
| CN110117235B (en) | Compound with aggregation-induced light emission and mechanochromism characteristics and preparation method and application thereof | |
| CN110551292A (en) | preparation method of rare earth luminescent material with adjustable light color | |
| Zheng et al. | Photosensitivity enhancement of spiropyran-containing functional molecules by introducing flexible spacers and their application in smart color-changing textiles | |
| CN109293646B (en) | Organic photochromic material and preparation method and application thereof | |
| CN110041226B (en) | Compound with AIE characteristics and preparation method and application thereof | |
| CN102887915A (en) | Heteronuclear bimetallic complex light-emitting material and preparation method and application thereof | |
| CN105152973A (en) | Stilbene derivative as well as preparation method and application thereof | |
| CN116375673B (en) | Bimodal fluorescent material with mechanochromism and preparation method thereof | |
| CN115181056B (en) | Fluorescent organic CNS and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |