CN105524085A - 1, 4-dimethyl-2, 5-dimethylene bistriazole terephthalic acid three-dimensional zinc complex single crystal and application thereof - Google Patents
1, 4-dimethyl-2, 5-dimethylene bistriazole terephthalic acid three-dimensional zinc complex single crystal and application thereof Download PDFInfo
- Publication number
- CN105524085A CN105524085A CN201610001100.5A CN201610001100A CN105524085A CN 105524085 A CN105524085 A CN 105524085A CN 201610001100 A CN201610001100 A CN 201610001100A CN 105524085 A CN105524085 A CN 105524085A
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- terephthalic acid
- tpa
- triazole
- single crystal
- 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.)
- Pending
Links
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000013078 crystal Substances 0.000 title claims abstract description 25
- 239000011701 zinc Substances 0.000 title abstract 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract 3
- 229910052725 zinc Inorganic materials 0.000 title abstract 3
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 239000000975 dye Substances 0.000 claims description 20
- 150000003852 triazoles Chemical class 0.000 claims description 14
- 230000000274 adsorptive effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 15
- IYWWVPFEBVKLBK-UHFFFAOYSA-N 1-[2,5-dimethyl-4-(1,2,4-triazol-1-yl)phenyl]-1,2,4-triazole Chemical compound CC1=C(C=C(C(=C1)N1N=CN=C1)C)N1N=CN=C1 IYWWVPFEBVKLBK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- NSPMIYGKQJPBQR-CVMUNTFWSA-N 1h-1,2,4-triazole Chemical class [13CH]=1[15N]=[13CH][15NH][15N]=1 NSPMIYGKQJPBQR-CVMUNTFWSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229960004643 cupric oxide Drugs 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
- 239000002994 raw material Substances 0.000 description 3
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-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
- 239000012065 filter cake Substances 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
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000967 suction filtration Methods 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
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical class CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-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
- 239000003153 chemical reaction reagent Substances 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
- 150000002894 organic compounds Chemical class 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- 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
- C09K2211/1018—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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention discloses a 1,4-dimethyl-2,5-dimethylene-bistriazole terephthalic acid three-dimensional zinc complex single crystal and application thereof, the structure is shown as [Zn (L) (tpa)]. MPD, wherein L = 1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl) phenyl )-1H-1,2,4-triazole; tpa = terephthalic acid; and MPD = 1-methyl-2-pyrrolidinone. The present invention also discloses a method for preparing the single crystal. A normal temperature volatilization method is used, to be more specific, L, Zn (NO3) 2.6H2O and tpa are stirred in a mixed solvent of water and MPD for half an hour and then filtered, and the filtrate is volatilized at normal temperature for two weeks to obtain a colorless bulk crystal suitable for X-ray single crystal diffraction, wherein molar ratio of L to Zn (NO3) 2.6H2O to tpa is 1: 1: 1. The present invention further discloses application of the 1,4-dimethyl-2,5-dimethylene-bistriazole terephthalic acid three-dimensional zinc complex single crystal as a potential fluorescent material in detection of adsorption quantity of a dye or an emitting agent.
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 1, three-dimensional Zn complex monocrystalline [Zn (L) (the tpa)] preparation method of MPD of the two triazole terephthalic acid of 4-dimethyl-2,5-dimethylene and the application as potential fluorescent material, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole; Tpa=terephthalic acid; MPD=1-N-methyl-2-2-pyrrolidone N-.
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 Zn (NO
3)
26H
2o filters stir half an hour in the mixed solvent of water and MPD after, filtrate normal temperature obtains applicable X-ray single crystal diffraction colourless bulk crystal structure after volatilizing two weeks is [Zn (L) (tpa)] MPD, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole; Tpa=terephthalic acid; MPD=1-N-methyl-2-2-pyrrolidone N-.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 1,4-dimethyl-2, the monocrystalline of the three-dimensional Zn complex of the two triazole terephthalic acid of 5-dimethylene, 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, collects point diffraction 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:
[Zn (L) (tpa)] MPD, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole;
Tpa=terephthalic acid; MPD=1-N-methyl-2-2-pyrrolidone N-.
The present invention further discloses the preparation method of the three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene, it is characterized in that it adopts normal temperature volatilization method, by L, tpa and Zn (NO
3)
26H
2o filters stir half an hour in the mixed solvent of water and MPD after, and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:tpa:Zn (NO
3)
26H
2the mol ratio of O is 1:1:1;
The structure of the three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene is [Zn (L) (tpa)]; Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole; Tpa=terephthalic acid; MPD=1-N-methyl-2-2-pyrrolidone N-;
LtpaMPD。
The present invention further discloses the three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene 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 preparation of 1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L)
Bromo-2, the 5-dimethyl benzenes of Isosorbide-5-Nitrae-two: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1
CuO (0.0398mg, 0.5mmol) is added respectively, salt of wormwood (2.0731g in 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 15mmol), 1H-1,2,4-triazole (0.345mg, 5mmol), bromo-2, the 5-dimethyl benzene (0.3360g of Isosorbide-5-Nitrae-two, 1mmol), 20mLDMF.Start and be stirred in 100
oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, filter, filtrate adds 100mL water, separates out and precipitates in a large number, suction filtration, collects filter cake, yield 60%.Ultimate analysis (C
12n
6h
12) theoretical value (%): C, 59.99; H, 5.03; N, 34.98.Measured value: C, 60.02; H, 5.05; N, 35.05;
Bromo-2, the 5-dimethyl benzene 1H-1 of Isosorbide-5-Nitrae-two, 2,4-triazole
Bromo-2, the 5-dimethyl benzenes of the preferred Isosorbide-5-Nitrae of the present invention-two: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour.
Another preferred embodiment of the present invention
1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L) (0.1mmol), terephthalic acid (tpa) (0.1mmol) and Zn (NO
3)
26H
2o (0.1mmol) filters stir half an hour in the mixed solvent of water (4mL) and 1-Methyl-2-Pyrrolidone (MPD) (6mL) after, and 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
25h
25n
7o
5zn) theoretical value (%): C, 52.78; H, 4.43; N, 17.23.Measured value: C, 52.95; H, 4.55; N, 17.02.
The advantage and disadvantage that the three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of a kind of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene 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 three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2, the 5-dimethylene 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 tomograph 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 all have commercially available.The raw materials such as all raw materials are all buy from chemical reagents corporation both domestic and external, such as bromo-2, the 5-dimethyl benzenes of Isosorbide-5-Nitrae-two, through continuation purify but directly use.
Embodiment 1
Bromo-2, the 5-dimethyl benzenes of Isosorbide-5-Nitrae-two: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1
CuO (0.0398mg, 0.5mmol) is added respectively, salt of wormwood (2.0731g in 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 15mmol), 1H-1,2,4-triazole (0.345mg, 5mmol), bromo-2, the 5-dimethyl benzene (0.3360g of Isosorbide-5-Nitrae-two, 1mmol), 20mLDMF.Start and be stirred in 100
oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, filter, filtrate adds 100mL water, separates out and precipitates in a large number, suction filtration, collects filter cake, yield 60%.Ultimate analysis (C
12n
6h
12) theoretical value (%): C, 59.99; H, 5.03; N, 34.98.Measured value: C, 60.02; H, 5.05; N, 35.05;
Bromo-2, the 5-dimethyl benzene 1H-1 of Isosorbide-5-Nitrae-two, 2,4-triazole.
Bromo-2, the 5-dimethyl benzenes of the preferred Isosorbide-5-Nitrae of the present invention-two: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour.Adopt " one kettle way ", by bromo-for Isosorbide-5-Nitrae-two 2,5-dimethyl benzenes and 1H-1,2,4-triazole prepares this organic compound in a heated condition, 1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L).
Embodiment 2
1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L) (0.1mmol), terephthalic acid (tpa) (0.1mmol) and Zn (NO
3)
26H
2o (0.1mmol) filters stir half an hour in the mixed solvent of water (4mL) and 1-Methyl-2-Pyrrolidone (MPD) (6mL) after, and 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
25h
25n
7o
5zn) theoretical value (%): C, 52.78; H, 4.43; N, 17.23.Measured value: C, 52.95; H, 4.55; N, 17.02.
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
The three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene 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: two for Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene triazole terephthalic acids three-dimensional Zn 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. one kind 1,4-dimethyl-2, the monocrystalline of the three-dimensional Zn complex of the two triazole terephthalic acid of 5-dimethylene, 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, collects point diffraction 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:
[Zn (L) (tpa)] MPD, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole;
Tpa=terephthalic acid; MPD=1-N-methyl-2-2-pyrrolidone N-.
2. the preparation method of the three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene described in claim 1, is characterized in that it adopts normal temperature volatilization method, by L, tpa and Zn (NO
3)
26H
2o filters stir half an hour in the mixed solvent of water and MPD after, and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:tpa:Zn (NO
3)
26H
2the mol ratio of O is 1:1:1;
The structure of the three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene is [Zn (L) (tpa)] MPD; Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole; Tpa=terephthalic acid; MPD=1-N-methyl-2-2-pyrrolidone N-;
LtpaMPD。
3. the three-dimensional Zn complex monocrystalline of the two triazole terephthalic acid of Isosorbide-5-Nitrae-dimethyl-2,5-dimethylene described in claim 1 is as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610001100.5A CN105524085A (en) | 2016-01-05 | 2016-01-05 | 1, 4-dimethyl-2, 5-dimethylene bistriazole terephthalic acid three-dimensional zinc complex single crystal and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610001100.5A CN105524085A (en) | 2016-01-05 | 2016-01-05 | 1, 4-dimethyl-2, 5-dimethylene bistriazole terephthalic acid three-dimensional zinc complex single crystal and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105524085A true CN105524085A (en) | 2016-04-27 |
Family
ID=55766647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610001100.5A Pending CN105524085A (en) | 2016-01-05 | 2016-01-05 | 1, 4-dimethyl-2, 5-dimethylene bistriazole terephthalic acid three-dimensional zinc complex single crystal and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105524085A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336687A (en) * | 2021-05-20 | 2021-09-03 | 东南大学 | Method for preparing 3-pyrroline based on improved activated zinc powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610302A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Antharcycline bis-triazole terephthalic acid zinc complex with potential fluorescent material and preparation method of antharcycline bis-triazole terephthalic acid zinc complex |
| CN104628750A (en) * | 2015-02-26 | 2015-05-20 | 天津师范大学 | Anthracene ring bis-triazole zinc complex with potential fluorescent material and preparation method thereof |
-
2016
- 2016-01-05 CN CN201610001100.5A patent/CN105524085A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610302A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Antharcycline bis-triazole terephthalic acid zinc complex with potential fluorescent material and preparation method of antharcycline bis-triazole terephthalic acid zinc complex |
| CN104628750A (en) * | 2015-02-26 | 2015-05-20 | 天津师范大学 | Anthracene ring bis-triazole zinc complex with potential fluorescent material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 苗少斌: "基于1,2,4-三氮唑配体的配位聚合物的合成、结构和性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336687A (en) * | 2021-05-20 | 2021-09-03 | 东南大学 | Method for preparing 3-pyrroline based on improved activated zinc powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105418647A (en) | Anthracene nucleus di-triazole three-dimensional copper nitrate complex single crystal and application | |
| CN105418657A (en) | 1,4-dimethyl-2,5-dimethylene bis(triazole)isophthalic acid-included dimethylacetamide cadimium complex single crystal and application | |
| CN105418659A (en) | 1,4-dimethyl-2,5-dimethylene bis triazol hydroxyphenylacetic isophthalic acid cadmium complex single crystal and application | |
| CN105524123A (en) | 1, 4-dimethyl-2, 5-dimethylene bistriazole nickel complex single crystal and application thereof | |
| CN105418654A (en) | 1,4-dimethyl-2,5-dimethylene bis(triazole) 5-methyl isophthalic acid cadimium complex single crystal and application | |
| CN105566361A (en) | 1,4-dibromo-2,5-dimethylene bis(triazole) cadmium complex monocrystal and applications thereof | |
| CN105669726A (en) | 4H-oxyether bistriazol cadmium complex monocrystal, and preparation method and application thereof | |
| CN105566360A (en) | Tetraphenyl ethylene tetra(triazole) inclusion dimethyl acetamide cadmium complex and preparation method thereof | |
| CN105541881A (en) | 1,4-dimethyl-2,5-dimethylene bis(triazole) three-dimensional cadmium complex single crystal and application | |
| CN105524094A (en) | 1, 4-dimethyl-2, 5-dimethylene bistriazole inclusion N, N'-diethyl acetamide cadmium complex single crystal | |
| CN105524119A (en) | 1, 4-dimethyl-2, 5-dimethylene bistriazole ferrous complex single crystal and application thereof | |
| CN105418649A (en) | Two-dimensional zinc 4H thioether bis(triazole) complex single crystal as well as preparation method and application thereof | |
| CN105541882A (en) | 2,5-dibromo-1,4-biphenoxyl bi(acetic acid) cadmium acetate complex single crystal and application | |
| CN105524085A (en) | 1, 4-dimethyl-2, 5-dimethylene bistriazole terephthalic acid three-dimensional zinc complex single crystal and application thereof | |
| CN105524091A (en) | 1, 4-dimethyl-2, 5-dimethylene bistriazole zinc complex single crystal and application thereof | |
| CN105524098A (en) | 1, 4-dimethyl-2, 5-dimethylene bistriazole isophthalic acid cadmium complex single crystal and application thereof | |
| CN105566359A (en) | 1,4-dimethyl-2,5-dimethylene bis(triazole) zinc terephthalate complex monocrystal and applications thereof | |
| CN105418658A (en) | 1,4-dimethyl-2,5-dimethylene bis triazol one-dimensional cadmium complex single crystal and application | |
| CN105418523A (en) | 1,4-dimethyl-2,5-dimethylene bis(triazole)terephthalic acid single crystal and application | |
| CN105503913A (en) | 1, 4-dimethyl-2, 5-dimethylene bis triazole cadmium terephthalate complex single crystal and application | |
| CN105418688A (en) | 1,4-dimethyl-2,5-dimethylene bis triazol three-dimensional nickel complex single crystal and application | |
| CN105418652A (en) | 1,4-dibromo-2,5-dimethylene bis triazol hydroxyphenylacetic isophthalic acid zinc complex single crystal and application | |
| CN105418656A (en) | Anthracene nucleus di-triazole isophthalic acid included diethyl formamide cadmium complex single crystal and application | |
| CN105622653A (en) | 1,4-dimethyl-2,5-dimethylene bistriazole terephthalic acid three-dimensional cadmium complex single crystal and application thereof | |
| CN105418651A (en) | Potential fluorescent material tetraphenyl ethylene tetratriazole zinc silicofluoride complex and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160427 |
|
| RJ01 | Rejection of invention patent application after publication |