CN105418655A - Potential fluorescent material tetraphenyl ethylene tetratriazole cadmium terephthalate complex and preparing method thereof - Google Patents
Potential fluorescent material tetraphenyl ethylene tetratriazole cadmium terephthalate complex and preparing method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title claims abstract description 8
- -1 tetraphenyl ethylene tetratriazole cadmium terephthalate Chemical compound 0.000 title abstract 3
- 239000013078 crystal Substances 0.000 claims abstract description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 20
- 150000003852 triazoles Chemical class 0.000 claims description 15
- MCQXGKSTPTWGSF-UHFFFAOYSA-N cadmium;terephthalic acid Chemical compound [Cd].OC(=O)C1=CC=C(C(O)=O)C=C1 MCQXGKSTPTWGSF-UHFFFAOYSA-N 0.000 claims description 14
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 8
- 230000000274 adsorptive effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 abstract 2
- QZZGHWFLUFTTOI-UHFFFAOYSA-N 1-[4-[1,2,2-tris[4-(1,2,4-triazol-1-yl)phenyl]ethenyl]phenyl]-1,2,4-triazole Chemical group C1=NN(C=N1)C1=CC=C(C=C1)C(=C(C1=CC=C(C=C1)N1C=NC=N1)C1=CC=C(C=C1)N1C=NC=N1)C1=CC=C(C=C1)N1C=NC=N1 QZZGHWFLUFTTOI-UHFFFAOYSA-N 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 18
- BIRLDGKMJJEZRI-UHFFFAOYSA-N 1-bromo-4-[1,2,2-tris(4-bromophenyl)ethenyl]benzene Chemical compound C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)=C(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 BIRLDGKMJJEZRI-UHFFFAOYSA-N 0.000 description 11
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229960004643 cupric oxide Drugs 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 9
- 235000015320 potassium carbonate Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- NSPMIYGKQJPBQR-CVMUNTFWSA-N 1h-1,2,4-triazole Chemical class [13CH]=1[15N]=[13CH][15NH][15N]=1 NSPMIYGKQJPBQR-CVMUNTFWSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a tetraphenyl ethylene tetratriazole cadmium terephthalate complex single crystal and a preparing method and application thereof. The structure of the complex single crystal is [Cd(L)(tpa)(H2O)], wherein L represents 1,1,2,2-tetra[4-(1H-1,2,4-triazole-1-yl) phenyl] ethylene, and tpa represents terephthalic acid. The invention further discloses a preparing method of the single crystal. According to the preparing method, a normal temperature volatilization method is adopted, namely L, tpa and Cd(NO3)2.4H2O are stirred for half an hour in mixed solvent of CHCl3, CH3OH, water and N,N'-diethyl formamide and then filtered, and a colorless bulk crystal suitable for X-ray single crystal diffraction is obtained after filter liquor is volatilized at the normal temperature for two weeks, wherein the molar ratio of L:tpa:Cd(NO3)2.4H2O is 1:1:1. The invention further discloses application of the tetraphenyl ethylene tetratriazole cadmium terephthalate complex as a potential fluorescent material to detection of adsorbing capacity of dye or a luminescence reagent.
Description
The present invention obtains the subsidy that state natural sciences fund general project (21471113), Tianjin Education Commission general project (20140506) and Tianjin Normal University's Middl-age and youth faculty Academic innovations advance planning item (52XC1401).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline [Cd (L) (tpa) (H
2o) preparation method] and the application as potential fluorescent material, wherein, L=1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene; Tpa=terephthalic acid.
Background technology
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention adopts normal temperature volatilization method, i.e. L, tpa and Cd (NO
3)
24H
2o is at CHCl
3, CH
3the mixed solvent of OH, water and N, N'-diethylformamide filters after stirring half an hour, and filtrate normal temperature obtains applicable X-ray single crystal diffraction colourless bulk crystal structure after volatilizing two weeks is [Cd (L) (tpa) (H
2o)], wherein, L=1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene; Tpa=terephthalic acid.This title complex also can be used as potential fluorescent material aspect and is applied.
Summary of the invention
Current inventor provides following technical scheme for this reason:
A kind of monocrystalline of tetraphenyl ethylene four triazole terephthalic acid cadmium complex, it is characterized in that this single crystal structure adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, obtain unit cell parameters through least-squares refinement, utilize SHELXL-97 direct method to solve single crystal data from difference Fourier electron density map:
Its structure is as follows:
[Cd (L) (tpa) (H
2o)], wherein,
L=1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene;
Tpa=terephthalic acid.
The present invention further discloses the preparation method of tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline, its feature adopts normal temperature volatilization method in employing, i.e. L, tpa and Cd (NO
3)
24H
2o is at CHCl
3, CH
3the mixed solvent of OH, water and N, N'-diethylformamide filters after stirring half an hour, and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein, L:tpa:Cd (NO
3)
24H
2the mol ratio of O is 1:1:1;
The structure of tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline is [Cd (L) (tpa) (H
2o)]; Wherein L=1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene; Tpa=terephthalic acid;
Ltpa。
The present invention further discloses tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent, and experimental result shows:
(1) complex monocrystal in embodiment 2 has good selectivity and susceptibility to dyestuff, and detectability reaches 0.1ppm.
(2) can detect the luminous agent of trace, detection limit reaches 5.0 μ g/L.
(3) complex monocrystal that prepared by embodiment 2 is 1.4 × 10 for the adsorptive capacity of dyestuff
-3mol/cm
2.
The present invention's preferred example:
The present invention's preferred example:
The preparation of 1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene (L)
Adopt " one kettle way " at polar solvent, 1,1,2,2-tetra-(4-bromophenyl) ethene, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are reacted preparation in a heated condition; Wherein 1,1,2,2-tetra-(4-bromophenyl) ethene: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10-15:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour;
1,1,2,2-tetra-(4-bromophenyl) ethene 1H-1,2,4-triazole
The present invention is 1,1,2,2-tetra-(4-bromophenyl) ethene: 1H-1,2,4-triazole preferably: salt of wormwood: the mol ratio of cupric oxide is 2:10-15:30:1; Temperature of reaction 100 DEG C, 48 hours reaction times.In polar solvent, adopt " one kettle way ", by 1,1,2,2-tetra-(4-bromophenyl) ethene, 1H-1,2,4-triazole, salt of wormwood and cupric oxide prepare 1 in a heated condition, 1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene (L).Yield 60%.Ultimate analysis (C
34n
6h
24) theoretical value (%): C, 79.05; H, 4.68; N, 16.27.Measured value: C, 79.02; H, 4.65; N, 16.25.
Another preferred embodiment of the present invention
1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene (L) (0.1mmol), terephthalic acid (tpa) (0.1mmol) and Cd (NO
3)
24H
2o (0.1mmol) is at CHCl
3(1mL), CH
3filter after stirring half an hour in the mixed solvent of OH (4mL), water (4mL) and N, N'-diethylformamide (10mL), filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C
42h
30cdN
12o
5) theoretical value (%): C, 56.35; H, 3.38; N, 18.78.Measured value: C, 56.37; H, 3.45; N, 18.88.
The advantage and disadvantage that a kind of tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline disclosed by the invention has is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) the tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline prepared by the present invention, production cost is low, and method is easy, is applicable to scale operation.The photoelectric response range problem widening dyestuff can be solved at dyestuff or luminous agent application aspect.
Accompanying drawing explanation
Fig. 1: the crystalline structure figure of complex monocrystal;
Fig. 2: the two-dimensional layered structure figure of complex monocrystal.
Embodiment
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, never means that it limits the scope of the invention by any way.Raw materials used 1,1,2,2-tetra-(4-bromophenyl) ethene, 1H-1,2,4-triazole, salt of wormwood and cupric oxide etc. all have commercially available.All raw materials are all buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.
Embodiment 1
The preparation of 1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene (L)
Adopt " one kettle way " at polar solvent, 1,1,2,2-tetra-(4-bromophenyl) ethene, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are reacted preparation in a heated condition; Wherein 1,1,2,2-tetra-(4-bromophenyl) ethene: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10-15:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour;
1,1,2,2-tetra-(4-bromophenyl) ethene 1H-1,2,4-triazole
The present invention is 1,1,2,2-tetra-(4-bromophenyl) ethene: 1H-1,2,4-triazole preferably: salt of wormwood: the mol ratio of cupric oxide is 2:10-15:30:1; Temperature of reaction 100 DEG C, 48 hours reaction times.In polar solvent, adopt " one kettle way ", by 1,1,2,2-tetra-(4-bromophenyl) ethene, 1H-1,2,4-triazole, salt of wormwood and cupric oxide prepare 1 in a heated condition, 1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene (L).Yield 60%.Ultimate analysis (C
34n
6h
24) theoretical value (%): C, 79.05; H, 4.68; N, 16.27.Measured value: C, 79.02; H, 4.65; N, 16.25.
Embodiment 2
1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene (L) (0.1mmol), terephthalic acid (tpa) (0.1mmol) and Cd (NO
3)
24H
2o (0.1mmol) is at CHCl
3(1mL), CH
3filter after stirring half an hour in the mixed solvent of OH (4mL), water (4mL) and N, N'-diethylformamide (10mL), filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C
42h
30cdN
12o
5) theoretical value (%): C, 56.35; H, 3.38; N, 18.78.Measured value: C, 56.37; H, 3.45; N, 18.88.
Embodiment 3
Crystal structure determination adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, unit cell parameters is obtained through least-squares refinement, software is utilized to solve crystalline structure from difference Fourier electron density map, and through Lorentz lorentz and polarizing effect correction.All H atom are synthesized by difference Fourier and are determined through desirable position calculation.Detailed axonometry data:
Embodiment 4
The concrete instance that dyestuff or luminous agent use
Method: the PARSTAT2273 electrochemical workstation of differentiated pulse volt-ampere (DPV) the curve negotiating Princeton Applied Research Laboratory development of dye solution is measured.The DPV test of solution adopts three-electrode system, and glass-carbon electrode is working electrode, and supporting electrode is platinum plate electrode, homemade Ag/AgNO
3electrode is reference electrode; Electrolytic solution is the acetonitrile solution of 0.1molL-1TBAP.Reduce reversible point to for interior mark with Oxidation of Ferrocene, obtains the correction value between test system and standard hydrogen electrode system.
Monochromatic incident light photoelectric transformation efficiency (IPCE) describes the photoelectric transformation efficiency of DSCs under monochromatic ray effect, is transfer to the electronic number of external circuit and the ratio of incident light subnumber.During measurement, use 500W xenon lamp as light source, the monochromatic ray of incident light under the multifunctional assembled grating spectrograph of WDS-5 type obtains different wave length λ; Monochromatic light exposure, in the light anode of battery, reads current value I by Keithley2400 digital sourcemeter.Monochromatic good fortune illumination is measured by USB4000plug-and-play Miniature optical linear light spectrometer.
Step: in order to definitely understand dyestuff at TiO
2adsorptive capacity on film, complex monocrystal dye sensitization TiO prepared by embodiment 2
2(geometric area is about 1cm to nanometer crystal film
2) be immersed in 10mL0.01molL
-1sodium hydroxide methanol solution in spend the night, treat that the absorbancy of attached mensuration solution separated completely by dyestuff.Wash one's face and rinse one's mouth according to absorbancy and molar absorptivity and can calculate the adsorptive capacity of dyestuff on unit surface nanometer crystal film.The adsorptive capacity of this complex monocrystal is 1.4 × 10
-3mol/cm
2.
Result: compared with the methanol solution of dyestuff, complex monocrystal dyestuff is at TiO
2absorption spectrum on film all obviously broadens and red shift.This shows that dye molecule is at TiO
2define the J-aggregate of first also tail.From the principle of work of DSCs, the spectrum broadening that dye aggregation causes and red shift are very favourable for the widening of photoelectric response scope of dyestuff.But meanwhile, dye aggregation cognition reduces its electron injection efficiency greatly, thus causes the degraded performance of DSCs.So, in dye solution, usually add coadsorbent to suppress the gathering of dyestuff.This complex monocrystal is in methanol solution and at TiO
2the fluorometric investigation of the purple solution on membrane electrode adopts 2.5 × 10
-5the methanol solution of mol/L, maximum emission wavelength is positioned at 500nm.
Embodiment 5
Tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline is as the application preparing luminescent material.
Method: by spectrophotofluorometer, carries out the excitation wavelength of this compound monocrystal (embodiment 2) and the scanning of emission wavelength respectively, selects and determine optimal wavelength.
Conclusion: excitation wavelength and the emission wavelength of this compound are respectively 340nm and 500nm.
Step: tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline grinding compressing tablet is become the sheet sample that external diameter is 27mm, thickness is about 3mm, and the sample pool putting into MPF-4 fluorescence spectrophotometer is measured.
Result: the excitation wavelength lambda of this compound
ex=340nm, emission wavelength lambda
em=500nm.
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.And the present invention is not also by the restriction of example embodiment in specification sheets.
Claims (3)
1. the monocrystalline of a tetraphenyl ethylene four triazole terephthalic acid cadmium complex, it is characterized in that this single crystal structure adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, obtain unit cell parameters through least-squares refinement, utilize software to solve single crystal data from difference Fourier electron density map:
Its structure is as follows:
[Cd (L) (tpa) (H
2o)], wherein,
L=1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene;
Tpa=terephthalic acid.
2. the preparation method of tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline described in claim 1, is characterized in that it adopts normal temperature volatilization method, i.e. L, tpa and Cd (NO
3)
24H
2o is at CHCl
3, CH
3the mixed solvent of OH, water and N, N'-diethylformamide filters after stirring half an hour, and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein, L:tpa:Cd (NO
3)
24H
2the mol ratio of O is 1:1:1;
The structure of tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline is [Cd (L) (tpa) (H
2o)], wherein, L=1,1,2,2-tetra-[4-(1H-1,2,4-triazole-1-base) phenyl] ethene; Tpa=terephthalic acid;
Ltpa。
3. tetraphenyl ethylene four triazole terephthalic acid cadmium complex monocrystalline described in claim 1 is as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610321A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Tetraphenyl ethylene four triazole terephthalic acid cadmium complex with potential fluorescent material and preparation method thereof |
| CN104610312A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Tetraphenyl ethylene 4-triazole cadmium isophthalate complex serving as potential fluorescent material and preparation method thereof |
| CN104610320A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Fluorescent material containing tetraphenylethylene-4-triazole three-dimensional cadmium complex and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610321A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Tetraphenyl ethylene four triazole terephthalic acid cadmium complex with potential fluorescent material and preparation method thereof |
| CN104610312A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Tetraphenyl ethylene 4-triazole cadmium isophthalate complex serving as potential fluorescent material and preparation method thereof |
| CN104610320A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Fluorescent material containing tetraphenylethylene-4-triazole three-dimensional cadmium complex and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YAN YANG ET AL: "A Series of Coordination Polymers Constructed by Flexible 4‑Substituted Bis(1,2,4-triazole) Ligands and Polycarboxylate Anions:Syntheses, Structures, and Photoluminescent Properties", 《CRYST. GROWTH DES.》 * |
| 葛志伟等: "一个基于5-（2-吡啶基）-3，3′-联（1H-1，2，4-三氮唑）和均四苯甲酸的锌（II）超分子配合物的合成、晶体结构与荧光性质", 《天津师范大学学报（自然科学版）》 * |
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