CN105669725A - Anthracylbistriazolyl-m-phthalic acid inclusion dimethylacetamide cadmium complex monocrystal and application thereof - Google Patents
Anthracylbistriazolyl-m-phthalic acid inclusion dimethylacetamide cadmium complex monocrystal and application thereof Download PDFInfo
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- VTTFSNHZIRXHHF-UHFFFAOYSA-N [Cd].CC(=O)N(C)C Chemical compound [Cd].CC(=O)N(C)C VTTFSNHZIRXHHF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 21
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims description 19
- 150000003852 triazoles Chemical class 0.000 claims description 15
- 150000001454 anthracenes Chemical class 0.000 claims description 13
- 230000000274 adsorptive effect Effects 0.000 claims description 5
- 238000002360 preparation method 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
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- CPIYEXXYOQSGAM-UHFFFAOYSA-N 1-[10-(1,2,4-triazol-1-yl)anthracen-9-yl]-1,2,4-triazole Chemical compound C1=NN(C=N1)C1=C2C=CC=CC2=C(N2C=NC=N2)C2=CC=CC=C12 CPIYEXXYOQSGAM-UHFFFAOYSA-N 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-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 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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 7
- 229960004643 cupric oxide Drugs 0.000 description 7
- NSPMIYGKQJPBQR-CVMUNTFWSA-N 1h-1,2,4-triazole Chemical class [13CH]=1[15N]=[13CH][15NH][15N]=1 NSPMIYGKQJPBQR-CVMUNTFWSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 239000000047 product Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- -1 and after filtration Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical class C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 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
- 239000002798 polar solvent 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
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum 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
- 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000002994 raw material Substances 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
- 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
- G01N21/62—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"
-
- 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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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an anthracylbistriazolyl-m-phthalic acid inclusion dimethylacetamide cadmium complex monocrystal and an application thereof. The structure of the monocrystal is [Cd(L)(ipa)(DMAC)].H2O, wherein L is 1-[9-(1H-1,2,4-triazol-1-yl)anthracene-10-yl]-1H-1,2,4-triazole; ipa is m-phthalic acid; and DMAC is N,N'-dimethylacetamide. The method adopts a normal temperature volatilization technology, and concretely comprises the following steps: stirring Cd(NO3)2.6H2O, ipa and the L in a DMAC and water mixed solvent for 0.5h, filtering the obtained solution, and allowing the obtained filtrate to volatilize at normal temperature for 1 week in order to obtain the yellow rod-shaped crystal suitable for X-ray single crystal diffraction, wherein a molar ratio of Cd(NO3)2.6H2O to the ipa to the L is 1:1:1. The invention further discloses the application of the anthracylbistriazolyl-m-phthalic acid inclusion dimethylacetamide cadmium complex monocrystal in detection of the adsorption quantity of a dye or a luminescence agent as a potential fluorescent material.
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, it relates to state two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex [Cd (L) (ipa) (the DMAC)] H of anthracene nucleus2The preparation method of O and the application as potential fluorescent material, wherein, L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole; Ipa=m-phthalic acid; DMAC=N, N'-N,N-DIMETHYLACETAMIDE.
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 and metallic ion coordination on 2 form N1, N2-bridging pattern, for 4 do not replace 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this kind of N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class is seemingly. Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has a different dimension has been the most important step of device.
The present invention adopts normal temperature volatilization method, i.e. Cd (NO3)2·6H2O, ipa and L filter after stirring half an hour in the mixed solvent of DMAC and water, and filtrate normal temperature obtains yellow rhabdolith [Cd (L) (ipa) (the DMAC)] H of applicable X-ray single crystal diffraction after volatilizing one week2O, wherein, L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole; Ipa=m-phthalic acid; DMAC=N, N'-N,N-DIMETHYLACETAMIDE. This title complex also can be used as potential fluorescent material aspect and applied.
Summary of the invention
Current inventor provides following technical scheme for this reason:
The monocrystalline of the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex of a kind of anthracene nucleus, 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 monocrystalline data from difference fourier electron density map:
Its structure is as follows:
[Cd(L)(ipa)(DMAC)]·H2O, wherein
L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole;
Ipa=m-phthalic acid;
DMAC=N, N'-N,N-DIMETHYLACETAMIDE.
The present invention further discloses the preparation method of the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus, its feature in employing normal temperature volatilization method, by Cd (NO3)2·6H2O, ipa and L filter after stirring half an hour in the mixed solvent of DMAC and water, and filtrate normal temperature obtains the yellow rhabdolith of applicable X-ray single crystal diffraction after volatilizing one week; Wherein Cd (NO3)2·6H2The mol ratio of O:ipa:L is 1:1:1;
The structure of the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus is [Cd (L) (ipa) (DMAC)] H2O; Wherein L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole; Ipa=m-phthalic acid; DMAC=N, N'-N,N-DIMETHYLACETAMIDE;
Lipa。
The present invention further discloses the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus as the application of potential fluorescent material in the adsorptive capacity of detection dyestuff or luminous agent, and experimental result shows:
(1) dyestuff is had good selectivity and susceptibility by the complex monocrystal in embodiment 2, and detectability reaches 0.1ppm.
(2) can the luminous agent of detection 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/cm2。
The present invention's preferred example:
The preparation of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (L)
9,10-dibromoanthracene: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1
CuO (0.0398mg is added respectively in 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 0.5mmol), salt of wormwood (2.0731g, 15mmol), 1H-1,2,4-triazole (0.345mg, 5mmol), 9,10-dibromoanthracene (0.3360g, 1mmol) and 20mLDMF. Start and it is stirred in 100oC, reacts 24 hours. Reaction solution is down to room temperature after terminating by reaction, filters, and filtrate adds 100mL water, precipitates out and precipitates in a large number, takes out filter, collects filter cake, receipts rate 60%. Ultimate analysis (C18N6H12) theoretical value (%): C, 69.22; H, 3.87; N, 26.91. Measured value: C, 69.26; H, 3.99; N, 26.95;
9,10-dibromoanthracene 1H-1,2,4-triazole
The preferred 9,10-dibromoanthracene of the present invention: 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, 12-120 hour reaction times. In polar solvent, adopt " one kettle way ", by 9,10-dibromoanthracene, 1-[9-(1H-1 prepared in a heated condition by 1H-1,2,4-triazole, salt of wormwood and cupric oxide, 2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (L).
Another preferred embodiment of the present invention
1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (L) (0.1mmol), ipa (0.1mmol) and Cd (NO3)2·6H2O (0.1mmo) produces a small amount of yellow mercury oxide after stirring half an hour in 10mL water and 6mLDMAC mixed solvent, and after filtration, filtrate is yellow. Normal temperature has the yellow rhabdolith of applicable X-ray single crystal diffraction after volatilizing one week. Product rate: 35%. Ultimate analysis (C30H28CdN7O6) theoretical value (%): C, 51.84; H, 4.06; N, 14.11. Measured value: C, 51.92; H, 3.94; N, 14.02.
The advantage and disadvantage that the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of a kind of anthracene nucleus disclosed by the invention has is:
(1) operation is simple and easy to do.
(2) reaction yield height, the purity height of products obtained therefrom.
(3) the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus 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 9,10-dibromoanthracene, 1H-1,2,4-triazole, salt of wormwood and cupric oxide etc. all have commercially available, directly buy, it does not have through continuing to purify and directly use.
Embodiment 1
The preparation of 1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (L)
9,10-dibromoanthracene: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1
CuO (0.0398mg is added respectively in 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 0.5mmol), salt of wormwood (2.0731g, 15mmol), 1H-1,2,4-triazole (0.345mg, 5mmol), 9,10-dibromoanthracene (0.3360g, 1mmol) and 20mLDMF. Start and it is stirred in 100oC, reacts 24 hours. Reaction solution is down to room temperature after terminating by reaction, filters, and filtrate adds 100mL water, precipitates out and precipitates in a large number, takes out filter, collects filter cake, receipts rate 60%. Ultimate analysis (C18N6H12) theoretical value (%): C, 69.22; H, 3.87; N, 26.91. Measured value: C, 69.26; H, 3.99; N, 26.95;
9,10-dibromoanthracene 1H-1,2,4-triazole
The preferred 9,10-dibromoanthracene of the present invention: 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, 12-120 hour reaction times. In polar solvent, adopt " one kettle way ", by 9,10-dibromoanthracene, 1-[9-(1H-1 prepared in a heated condition by 1H-1,2,4-triazole, salt of wormwood and cupric oxide, 2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (L).
Embodiment 2
1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (L) (0.1mmol), ipa (0.1mmol) and Cd (NO3)2·6H2O (0.1mmo) produces a small amount of yellow mercury oxide after stirring half an hour in 10mL water and 6mLDMAC mixed solvent, and after filtration, filtrate is yellow. Normal temperature has the yellow rhabdolith of applicable X-ray single crystal diffraction after volatilizing one week. Product rate: 35%. Ultimate analysis (C30H28CdN7O6) theoretical value (%): C, 51.84; H, 4.06; N, 14.11. Measured value: C, 51.92; H, 3.94; N, 14.02.
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/AgNO3Electrode is reference electrode; Electrolytic solution is the acetonitrile solution of 0.1mol L-1TBAP. Taking ferrocene redox reversible point to as interior mark, obtain 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 the ratio of electronic number and the incident light subnumber transferring to external circuit. During measurement, it may also be useful to 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 ray is irradiated in the light anode of battery, reads current value I by Keithley2400 digital sourcemeter. The good fortune illumination of monochromatic ray is measured by USB4000plug-and-play Miniature optical line spectrum instrument.
Step: in order to definitely understand dyestuff at TiO2Adsorptive capacity on film, complex monocrystal dye sensitization TiO prepared by embodiment 22(geometry area is about 1cm to nanometer crystal film2) it is immersed in 10mL0.01mol L-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/cm2。
Result: compared with the methanol solution of dyestuff, complex monocrystal dyestuff is at TiO2Absorption spectrum on film all obviously becomes wide and red shift. This shows that dye molecule is at TiO2Define the J-aggregate of first also tail. From the principle of work of DSCs, spectrum broadening that dye aggregation causes and red shift are very favourable for the widening of photoelectric response scope of dyestuff. Meanwhile, but, 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 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 two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus 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 anthracene nucleus triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline grinding compressing tablet becomes external diameter be the sheet sample that 27mm, thickness are about 3mm, and the sample pool putting into MPF-4 fluorescence spectrophotometer is measured.
Result: the excitation wavelength lambda of this compoundex=340nm, emission wavelength lambdaem=500nm。
After the better embodiment illustrated in detail, it is familiar with this skilled worker can be well understood to, do not depart from above-mentioned claim with spirit under can carry out various change and amendment, all any simple modification, equivalent variations and modifications above embodiment done according to the technical spirit of the present invention, all belong to the scope of technical solution of the present invention. And the present invention does not also implement the restriction of mode by example in specification sheets.
Claims (3)
1. the monocrystalline of the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex of anthracene nucleus, 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 monocrystalline data from difference fourier electron density map:
Its structure is as follows:
[Cd(L)(ipa)(DMAC)]·H2O, wherein
L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole;
Ipa=m-phthalic acid;
DMAC=N, N'-N,N-DIMETHYLACETAMIDE.
2. the preparation method of the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus described in claim 1, it is characterised in that it adopts normal temperature volatilization method, i.e. Cd (NO3)2·6H2O, ipa and L filter after stirring half an hour in the mixed solvent of DMAC and water, and filtrate normal temperature obtains the yellow rhabdolith of applicable X-ray single crystal diffraction after volatilizing one week; Wherein Cd (NO3)2·6H2The mol ratio of O:ipa:L is 1:1:1;
The structure of the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus is [Cd (L) (ipa) (DMAC)] H2O, wherein, L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole; Ipa=m-phthalic acid; DMAC=N, N'-N,N-DIMETHYLACETAMIDE;
Lipa。
3. the two triazole m-phthalic acid inclusion N,N-DIMETHYLACETAMIDE cadmium complex monocrystalline of anthracene nucleus described in claim 1 is as the application of potential fluorescent material in the adsorptive capacity of detection dyestuff or luminous agent.
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| CN104592265A (en) * | 2015-02-26 | 2015-05-06 | 天津师范大学 | Cadmium phthalate anthracene cyclo-bis(triazolyl) complex used as potential fluorescent material and preparation method of cadmium phthalate anthracene cyclo-bis(triazolyl) complex |
| CN104610318A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Antharcycline bis-triazole cadmium complex with potential fluorescent material and preparation method of antharcycline dual triazole cadmium complex |
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