CN105566356A - 4H-oxo-ether bis(triazole) trinuclear copper complex monocrystal, preparation method and applications thereof - Google Patents
4H-oxo-ether bis(triazole) trinuclear copper complex monocrystal, preparation method and applications thereof Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 16
- 150000003852 triazoles Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000975 dye Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000000274 adsorptive effect Effects 0.000 claims description 5
- 238000012937 correction Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000005260 alpha ray Effects 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 abstract 2
- VAIPDCSLQLVVDH-UHFFFAOYSA-N 4-[4-[4-(1,2,4-triazol-4-yl)phenoxy]phenyl]-1,2,4-triazole Chemical compound N=1N=CN(C1)C1=CC=C(OC2=CC=C(C=C2)N2C=NN=C2)C=C1 VAIPDCSLQLVVDH-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 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
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 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
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 oxygen ether triazole Chemical class 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
- 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
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a 4H-oxo-ether bis(triazole) trinuclear copper complex monocrystal. The chemical structural formula of the monocrystal is [Cu3(SO4)(L)3(H2O)2](SO4)2.2H2O; wherein the L represents 4-(4-(4-(4H-1,2,4-triazole-4-yl)phenoxyl)phenyl)-4H-1,2,4-triazole. The invention also discloses a preparation method of the monocrystal. The preparation method adopts a room temperature volatilization technology, and comprises the following steps: adding L, and CuSO4.5H2O into water, stirring for an half hour, filtering, and volatilizing the filtrate at a room temperature for two weeks to obtain blue block-like crystals suitable for X-ray single crystal diffraction; wherein the mole ratio of L: CuSO4.5H2O is 1:2. The invention further discloses applications of the4H-oxo-ether bis(triazole) trinuclear copper complex monocrystal as a potential fluorescent material in the detection of adsorption amount of dyes or illuminating 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 the two triazole three core copper complex monocrystalline [Cu of 4H oxygen ether
3(SO
4) (L)
3(H
2o)
2] (SO
4)
22H
2the preparation method of O and the application as potential fluorescent material, wherein, L=4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole.
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 and CuSO
45H
2o filters stir half an hour in water after, and filtrate normal temperature obtains applicable X-ray single crystal diffraction blue bulk crystal structure after volatilizing two weeks is [Cu
3(SO
4) (L)
3(H
2o)
2] (SO
4)
22H
2o, wherein, L=4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole.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:
Its structure is as follows:
[Cu
3(SO
4) (L)
3(H
2o)
2] (SO
4)
22H
2o, wherein
L=4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole.
The present invention further discloses the preparation method of the two triazole three core copper complex monocrystalline of 4H oxygen ether, it is characterized in that it adopts normal temperature volatilization method, by L and CuSO
45H
2o filters stir half an hour in water after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:CuSO
45H
2the mol ratio of O is 1:1;
The structure of the two triazole three core copper complex monocrystalline of 4H oxygen ether is [Cu
3(SO
4) (L)
3(H
2o)
2] (SO
4)
22H
2o; Wherein L=4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole;
L。
The present invention further discloses the two triazole three core copper complex monocrystalline of 4H oxygen ether as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent
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 4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole (L)
4-(4-amino-benzene oxygen) aniline: the mol ratio of two formyl hydrazine is 1:4
In 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add 4-(4-amino-benzene oxygen) aniline (1mmol) and two formyl hydrazine (4mmol) respectively, start and be stirred in 150
oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, the precipitation obtained is added 100mL hot methanol, after stirring and dissolving, filter, filtrate is slowly volatilized and is obtained white solid, yield 85%;
The two formyl hydrazine of 4-(4-amino-benzene oxygen) aniline.
The mol ratio of the preferred 4-of the present invention (4-amino-benzene oxygen) aniline and two formyl hydrazine is 1:4; Temperature of reaction 150 DEG C, 24 hours reaction times.Adopt " one kettle way ", 4-(4-amino-benzene oxygen) aniline and two formyl hydrazine are prepared 4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1 in a heated condition, 2,4-triazole (L).Ultimate analysis (C
64h
56n
24o
8) measured value: C59.62; H4.38; N26.07.Theoretical value: C59.68; H4.40; N26.13.
Another preferred embodiment of the present invention
4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole (L) (0.1mmol) and CuSO
45H
2o (0.2mmol) filters stir half an hour in water (10mL) after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C
48h
44cu
3n
18o
19s
3) theoretical value (%): C, 39.38; H, 3.03; N, 17.22.Measured value: C, 39.45; H, 3.14; N, 17.09.
The advantage and disadvantage that the two triazole three core copper complex monocrystalline of a kind of 4H oxygen ether 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 two triazole three core copper complex monocrystalline of the 4H oxygen ether 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.All raw material 4-(4-amino-benzene oxygen) aniline and CuSO
45H
2o etc. buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.
Embodiment 1
4-(4-amino-benzene oxygen) aniline: the mol ratio of two formyl hydrazine is 1:4
In 50mL tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, add 4-(4-amino-benzene oxygen) aniline (1mmol) and two formyl hydrazine (4mmol) respectively, start and be stirred in 150
oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, the precipitation obtained is added 100mL hot methanol, after stirring and dissolving, filter, filtrate is slowly volatilized and is obtained white solid, yield 85%;
The two formyl hydrazine of 4-(4-amino-benzene oxygen) aniline.
The mol ratio of the preferred 4-of the present invention (4-amino-benzene oxygen) aniline and two formyl hydrazine is 1:4; Temperature of reaction 150 DEG C, 24 hours reaction times.Adopt " one kettle way ", 4-(4-amino-benzene oxygen) aniline and two formyl hydrazine are prepared 4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1 in a heated condition, 2,4-triazole (L).Ultimate analysis (C
64h
56n
24o
8) measured value: C59.62; H4.38; N26.07.Theoretical value: C59.68; H4.40; N26.13.
Embodiment 2
4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole (L) (0.1mmol) and CuSO
45H
2o (0.2mmol) filters stir half an hour in water (10mL) after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C
48h
44cu
3n
18o
19s
3) theoretical value (%): C, 39.38; H, 3.03; N, 17.22.Measured value: C, 39.45; H, 3.14; N, 17.09.
Embodiment 3
Crystal structure determination adopts APEXIICZN 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 two triazole three core copper complex monocrystalline of 4H oxygen ether 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 4H oxygen ether triazole three core copper complex monocrystalline grinding compressing tablet is become the sheet sample that external diameter is 27mm, thickness is about 3mm, and the sample pool putting into MPF-4 fluorescence spectrophotometer is measured.
Result: the excitation wavelength lambda of this compound
ex=340nm, emission wavelength lambda
em=500nm.
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.And the present invention is not also by the restriction of example embodiment in specification sheets.
Claims (3)
1. the monocrystalline of two triazole three core copper complex of 4H oxygen ether, it is characterized in that this single crystal structure adopts APEXIICZN 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:
Its structure is as follows:
[Cu
3(SO
4) (L)
3(H
2o)
2] (SO
4)
22H
2o, wherein
L=4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole.
2. the preparation method of the two triazole three core copper complex monocrystalline of 4H oxygen ether described in claim 1, is characterized in that it adopts normal temperature volatilization method, by L and CuSO
45H
2o filters stir half an hour in water after, and filtrate normal temperature obtains the blue bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:CuSO
45H
2the mol ratio of O is 1:2;
The structure of the two triazole three core copper complex monocrystalline of 4H oxygen ether is [Cu
3(SO
4) (L)
3(H
2o)
2] (SO
4)
22H
2o; Wherein L=4-(4-(4-(4H-1,2,4-triazole-4-yl) phenoxy group) phenyl)-4H-1,2,4-triazole;
L。
3. the two triazole three core copper complex monocrystalline of 4H oxygen ether described in claim 1 is as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent.
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| CN201610001163.0A CN105566356A (en) | 2016-01-05 | 2016-01-05 | 4H-oxo-ether bis(triazole) trinuclear copper complex monocrystal, preparation method and applications thereof |
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| CN106187925A (en) * | 2016-07-28 | 2016-12-07 | 天津师范大学 | The double triazole terephthalic acid compounds monocrystalline of 4H thioether and application |
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| CN103965222A (en) * | 2013-01-28 | 2014-08-06 | 首都师范大学 | Trinuclear copper imidazole-4,5-dicarboxylic acid o-phenanthroline coordination compound, preparation method and application thereof |
| CN104610287A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether double-triazole one-dimensional copper complex with potential fluorescent material and preparation method thereof |
| CN104610286A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether bis-triazole copper bromide complex serving as potential fluorescent material and preparation method thereof |
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| CN104610287A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether double-triazole one-dimensional copper complex with potential fluorescent material and preparation method thereof |
| CN104610286A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether bis-triazole copper bromide complex serving as potential fluorescent material and preparation method thereof |
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| CN106187925A (en) * | 2016-07-28 | 2016-12-07 | 天津师范大学 | The double triazole terephthalic acid compounds monocrystalline of 4H thioether and application |
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