CN105622653A - 1,4-dimethyl-2,5-dimethylene bistriazole terephthalic acid three-dimensional cadmium complex single crystal and application thereof - Google Patents
1,4-dimethyl-2,5-dimethylene bistriazole terephthalic acid three-dimensional cadmium complex single crystal and application thereof Download PDFInfo
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- 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 28
- 239000013078 crystal Substances 0.000 title claims abstract description 26
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 17
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000975 dye Substances 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 150000003852 triazoles Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 7
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 230000008569 process Effects 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 abstract 4
- 238000004020 luminiscence type Methods 0.000 abstract 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- QXISTPDUYKNPLU-UHFFFAOYSA-N 2-bromo-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(Br)=C1 QXISTPDUYKNPLU-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 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
- QENIALCDPFDFHX-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethylbenzene Chemical compound CC1=CC(Br)=C(C)C=C1Br QENIALCDPFDFHX-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000005259 measurement Methods 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
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 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
- 230000009286 beneficial effect Effects 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
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a 1,4-dimethyl-2,5-dimethylene bistriazole terephthalic acid three-dimensional cadmium complex single crystal and an application thereof. The structural formula of the single crystal is [Cd(L)(tpa)] DEMC, wherein L is 1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-group) phenyl)-1H-1,2,4-triazole, tpa is terephthalic acid, and DEMC is N,N(minute)-diethyl formamide. The invention also discloses a preparation method of the single crystal. A normal temperature volatilization method is adopted, comprising mixing L, Cd(NO3)2 4H2O and tpa in a mixed solvent of water and DEMC for half an hour, filtering, and volatilizing filtrate at normal temperature for two weeks to obtain colorless bulk crystals suitable for X-ray single crystal diffraction, wherein the molar ratio of L to Cd(NO3)2 4H2O to tpa is 1 to 1 to 1. The invention also discloses an application of the 1,4-dimethyl-2,5-dimethylene bistriazole terephthalic acid three-dimensional cadmium complex single crystal as a potential fluorescent material to detection of adsorbing capacity of dyes or luminescence agents.
Description
The present invention obtains 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 and advances the subsidy of planning item (52XC1401).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to 1,4-dimethyl-2, the preparation method of double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline [Cd (L) (the tpa)] DEMC of 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-triazoles; Tpa=p-phthalic acid; DEMC=N, N'-diethylformamide.
Background technology
1,2,4-triazole and derivant thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridging ligands that coordination ability is stronger, have synthesized and characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present. These parts can with 1, nitrogen-atoms on 2 forms N1 with metallic ion coordination, N2-bridge gang mould formula, for 4 unsubstituted 1,2,4-triazole derivative can pass through 2, nitrogen-atoms on 4 forms N2, N4-bridge gang mould formula, this N2, N4-bridge gang mould formula is similar with N1, the N3-bridge gang mould formula of imidazoles in metalloenzyme. Specific use for triazole class compounds is also manifested by the design of molecular device, and it has been the vital step of device that synthesis has the metal complex of different dimension.
The present invention adopts room temperature volatility process, i.e. L, Cd (NO3)2��4H2O and tpa filters after stirring half an hour in the mixed solvent of water and DEMC, filtrate room temperature obtains being suitable for the colourless bulk crystal structure of X-ray single crystal diffraction after volatilizing two weeks be [Cd (L) (tpa)] DEMC, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazoles; Tpa=p-phthalic acid; DEMC=N, N'-diethylformamide. This coordination compound is alternatively arranged as potential fluorescent material aspect and is applied.
Summary of the invention
Following technical scheme is current inventor provides for this:
A kind of 1,4-dimethyl-2, the monocrystalline of the double; two triazole p-phthalic acid three-dimensional cadmium complex of 5-dimethylene, it is characterized in that this mono-crystalline structures adopts APEXIICNI single crystal diffractometer, using through graphite monochromatised Mok alpha ray, ��=0.71073 is incident radiation, collects point diffraction with ��-2 �� scan mode, obtain cell parameter through least square refinement, utilize software to solve single crystal data from difference Fourier electron density map:
Its structure is as follows:
[Cd (L) (tpa)] DEMC, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole;
Tpa=p-phthalic acid;
DEMC=N, N'-diethylformamide.
The present invention further discloses Isosorbide-5-Nitrae-dimethyl-2, the preparation method of the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 5-dimethylene, it is characterised in that it is to adopt room temperature volatility process, by L, Cd (NO3)2��4H2O and tpa filters after stirring half an hour in the mixed solvent of water and DEMC, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks; Wherein L:Cd (NO3)2��4H2The mol ratio of O:tpa is 1:1:1;
The structure of the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 1,4-dimethyl-2,5-dimethylene is [Cd (L) (tpa)] DEMC; Wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole; Tpa=p-phthalic acid; DEMC=N, N'-diethylformamide;
Ltpa��
The present invention further discloses Isosorbide-5-Nitrae-dimethyl-2, and the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 5-dimethylene is as the application in the adsorbance of detection dyestuff or luminous agent of the potential fluorescent material, and experimental result shows:
(1) dyestuff is had good selectivity and susceptiveness by the complex monocrystal in embodiment 2, and detection limit reaches 0.1ppm.
(2) can detecting the luminous agent of trace, detection limit reaches 5.0 �� g/L.
(3) complex monocrystal of embodiment 2 preparation is 1.4 �� 10 for the adsorbance of dyestuff-3mol/cm2��
One preferred example of the present invention:
The preparation of 1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L)
The bromo-2,5-dimethyl benzene of 1,4-bis-: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1
It is separately added into CuO (0.0398mg, 0.5mmol), potassium carbonate (2.0731g in equipped with tri-mouthfuls of round-bottomed flasks of 50mL of magneton, reflux condenser and thermometer, 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 stirring 100oC, reacts 24 hours. Reactant liquor is down to room temperature after terminating by reaction, filters, and filtrate adds 100mL water, precipitates out a large amount of precipitation, sucking filtration, collects filter cake, yield 60%. Elementary analysis (C12N6H12) theoretical value (%): C, 59.99; H, 5.03; N, 34.98. Measured value: C, 60.02; H, 5.05; N, 35.05;
1,4-bis-bromo-2,5-dimethyl benzene 1H-1,2,4-triazole
The bromo-2,5-dimethyl benzene of the preferred 1,4-of the present invention bis-: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1; Reaction temperature 80-200 DEG C, 12-120 hour response time.
Presently preferred embodiment
1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L) (0.1mmol), Cd (NO3)2��4H2O (0.1mmol) and tpa (0.1mmol) is at water (4mL) and N, in N'-diethylformamide (DEMC) (6mL), stirring was filtered after half an hour, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks. Productivity: 40%. Elementary analysis (C23H23CdN7O5) theoretical value (%): C, 46.83; H, 3.93; N, 16.62. Measured value: C, 46.58; H, 3.84; N, 16.68.
The double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline have the advantage that of a kind of 1,4-dimethyl-2,5-dimethylene disclosed by the invention and being characterized in that:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) Isosorbide-5-Nitrae-dimethyl-2 prepared by the present invention, the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 5-dimethylene, production cost is low, and method is easy, is suitable for large-scale production. Can solve to widen the photoelectric respone range problem of dyestuff at dyestuff or luminous agent application aspect.
Accompanying drawing explanation
Fig. 1: the crystal structure figure of complex monocrystal;
Fig. 2: the tomograph of complex monocrystal.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, is in no way to be construed as the scope that it is intended to limit the present invention in any manner. Raw materials used it is commercially available. All raw materials are all buy from chemical reagents corporation both domestic and external, for instance the raw materials such as bromo-2, the 5-dimethyl benzenes of Isosorbide-5-Nitrae-two, it does not have through continuation purify but directly use.
Embodiment 1
The bromo-2,5-dimethyl benzene of 1,4-bis-: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1
It is separately added into CuO (0.0398mg, 0.5mmol), potassium carbonate (2.0731g in equipped with tri-mouthfuls of round-bottomed flasks of 50mL of magneton, reflux condenser and thermometer, 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 stirring 100oC, reacts 24 hours. Reactant liquor is down to room temperature after terminating by reaction, filters, and filtrate adds 100mL water, precipitates out a large amount of precipitation, sucking filtration, collects filter cake, yield 60%. Elementary analysis (C12N6H12) theoretical value (%): C, 59.99; H, 5.03; N, 34.98. Measured value: C, 60.02; H, 5.05; N, 35.05;
1,4-bis-bromo-2,5-dimethyl benzene 1H-1,2,4-triazole.
The bromo-2,5-dimethyl benzene of the preferred 1,4-of the present invention bis-: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10:30:1; Reaction temperature 80-200 DEG C, 12-120 hour response time. Adopt " one kettle way ", by bromo-for Isosorbide-5-Nitrae-two 2,5-dimethyl benzenes and 1H-1,2,4-triazoles prepare this organic compound, 1-(2,5-dimethyl-4-(1H-1 in a heated condition, 2,4-triazol-1-yls) phenyl)-1H-1,2,4-triazoles (L).
1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole (L) (0.1mmol), Cd (NO3)2��4H2O (0.1mmol) and tpa (0.1mmol) is at water (4mL) and N, in N'-diethylformamide (DEMC) (6mL), stirring was filtered after half an hour, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks. Productivity: 40%. Elementary analysis (C23H23CdN7O5) theoretical value (%): C, 46.83; H, 3.93; N, 16.62. Measured value: C, 46.58; H, 3.84; N, 16.68.
Embodiment 3
Crystal structure determination adopts APEXIICNI single crystal diffractometer, use through graphite monochromatised Mok alpha ray, ��=0.71073 is incident radiation, point diffraction is collected with ��-2 �� scan mode, cell parameter is obtained through least square refinement, software is utilized to solve crystal structure from difference Fourier electron density map, and through Lorentz lorentz and polarity effect correction. All of H atom is synthesized by difference Fourier and determines through desirable position calculation. Detailed axonometry data:
Embodiment 4
The concrete instance that dyestuff or luminous agent use
Method: the PARSTAT2273 electrochemical workstation that differentiated pulse volt-ampere (DPV) the curve negotiating Princeton Applied Research Laboratory of dye solution is developed is measured. The DPV test of solution adopts three-electrode system, and glass-carbon electrode is working electrode, and auxiliary electrode is platinum plate electrode, homemade Ag/AgNO3Electrode is reference electrode; Electrolyte is the acetonitrile solution of 0.1mol L-1TBAP. Reduce reversible point to for interior mark with Oxidation of Ferrocene, obtains the corrected value between test system and standard hydrogen electrode system.
Monochromatic incident illumination photoelectric transformation efficiency (IPCE) describes DSCs photoelectric transformation efficiency under monochromatic light effect, is the ratio of the electron number transferring to external circuit and incident illumination subnumber. During measurement, using 500W xenon lamp as light source, incident illumination obtains the monochromatic light under different wave length �� through the multifunctional assembled grating spectrograph of WDS-5 type; Monochromatic light exposure, in the light anode of battery, is read 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 have any actual knowledge of dyestuff at TiO2Adsorbance on film, complex monocrystal dye sensitization TiO prepared by embodiment 22(geometric area is about 1cm to nanometer crystal film2) it is immersed in 10mL0.01mol L-1Sodium hydroxide methanol solution in overnight, treat that dyestuff solves the absorbance of attached mensuration solution completely. Wash one's face and rinse one's mouth according to absorbance and molar absorptivity and can calculate the adsorbance of dyestuff on unit are nanometer crystal film. The adsorbance of this complex monocrystal is 1.4 �� 10-3mol/cm2��
Result: compared with the methanol solution of dyestuff, complex monocrystal dyestuff is at TiO2Absorption spectrum on film all substantially broadens and red shift. This shows that dye molecule is at TiO2Define first and tail J-aggregation. From the operation principle of DSCs, spectrum broadening that dye aggregation causes and red shift are highly beneficial for the widening of photoelectric respone scope of dyestuff. But meanwhile, dye aggregation cognition is substantially reduced its electron injection efficiency, thus causing the degraded performance of DSCs. So, in dye solution, generally add coadsorbent suppress the gathering of dyestuff. This complex monocrystal is in methanol solution and at TiO2The 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 double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 1,4-dimethyl-2,5-dimethylene is as the application preparing luminescent material.
Method: by spectrofluorophotometer, carries out the excitation wavelength of this compound monocrystal (embodiment 2) respectively and launches the scanning of wavelength, select and determine optimal wavelength.
Conclusion: the excitation wavelength of this compound and transmitting wavelength respectively 340nm and 500nm.
Step: by Isosorbide-5-Nitrae-dimethyl-2, the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 5-dimethylene grinds tabletting and becomes external diameter to be the sheet sample that 27mm, thickness are about 3mm, puts into the sample cell measurement of MPF-4 fluorescence spectrophotometer.
Result: the excitation wavelength lambda of this compoundex=340nm, emission wavelength lambdaem=500nm��
After the preferred embodiment described in detail, it is familiar with this skilled worker to be clearly understood that, various change and amendment can be carried out under without departing from above-mentioned claim and spirit, all any simple modification, equivalent variations and modifications above example made according to the technical spirit of the present invention, 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 description.
Claims (3)
1. one kind 1,4-dimethyl-2, the monocrystalline of the double; two triazole p-phthalic acid three-dimensional cadmium complex of 5-dimethylene, it is characterized in that this mono-crystalline structures adopts APEXIICNI single crystal diffractometer, using through graphite monochromatised Mok alpha ray, ��=0.71073 is incident radiation, collects point diffraction with ��-2 �� scan mode, obtain cell parameter through least square refinement, utilize software to solve single crystal data from difference Fourier electron density map:
Its structure is as follows:
[Cd (L) (tpa)] DEMC, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole;
Tpa=p-phthalic acid; DEMC=N, N'-diethylformamide.
2. Isosorbide-5-Nitrae-dimethyl-2 described in claim 1, the preparation method of the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 5-dimethylene, it is characterised in that it is to adopt room temperature volatility process, by L, Cd (NO3)2��4H2O and tpa filters after stirring half an hour in the mixed solvent of water and DEMC, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks; Wherein L:Cd (NO3)2��4H2The mol ratio of O:tpa=is 1:1:1;
1,4-dimethyl-2, the structure of the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 5-dimethylene is [Cd (L) (tpa)] DEMC, wherein, L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazoles; Tpa=p-phthalic acid; DEMC=N, N'-diethylformamide
Ltpa��
3. the double; two triazole p-phthalic acid three-dimensional cadmium complex monocrystalline of 1,4-dimethyl-2,5-dimethylene described in claim 1 is as the application in the adsorbance of detection dyestuff or luminous agent of the potential fluorescent material.
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| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106220658A (en) * | 2016-07-28 | 2016-12-14 | 天津师范大学 | The double triazole two dimension cadmium complex monocrystalline of 1,2,4,5 durols and application |
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