CN104610368A - Oxygen ether double-triazole manganese complex with potential fluorescent material and preparation method thereof - Google Patents

Oxygen ether double-triazole manganese complex with potential fluorescent material and preparation method thereof Download PDF

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CN104610368A
CN104610368A CN201510088007.8A CN201510088007A CN104610368A CN 104610368 A CN104610368 A CN 104610368A CN 201510088007 A CN201510088007 A CN 201510088007A CN 104610368 A CN104610368 A CN 104610368A
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triazole
manganese complex
oxygen ether
chcl
phenyl
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王英
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Tianjin Normal University
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Tianjin Normal University
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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
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C07F13/005—Compounds without a metal-carbon linkage
    • 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
    • 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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  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses an oxygen ether double-triazole manganese complex {[Mn(L)2(N3)2].CHCl3} (1), of which the structural motif is showed in figure 1. Meanwhile the invention further discloses a preparation method for {[Mn(L)2(N3)2].CHCl3} (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl)phenoxy)phenyl)-1H-1,2,4-triazole). A normal temperature volatilization method is adopted by the method, namely L, Mn(ClO4)2.6H2O and NaN3 are added into a mixing solvent of CHCl3, CH3OH and water and are filtered after being stirred for half an hour, and two weeks after the filter liquor volatilizes at normal temperature, a colorless bulk crystal suitable for X-ray crystallography is obtained. The invention further discloses an application of the oxygen ether double-triazole manganese complex as a potential fluorescent material.

Description

Two triazole manganese complex of oxygen ether with potential fluorescent material and preparation method thereof
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to two triazole the manganese complex { [Mn (L) of oxygen ether 2(N 3) 2] CHCl 3( 1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) and the application as potential fluorescent material.
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 " diffusion process ", i.e. L, Mn (ClO 4) 26H 2o and NaN 3at CHCl 3, CH 3filter after stirring half an hour in the mixed solvent of OH and water, filtrate normal temperature volatilizees colourless the bulk crystals { [Mn (L) obtaining applicable X-ray single crystal diffraction for two weeks 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole).This title complex also can be used as potential fluorescent material aspect and is applied.
Summary of the invention
Another object of the present invention is to provide a kind of oxygen ether two triazole manganese complex { [Mn (L) 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Two triazole the manganese complex { [Mn (L) of oxygen ether 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) structural motif as shown in Figure 1.
The present invention further discloses two triazole the manganese complex { [Mn (L) of oxygen ether 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline, it is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize SHELXL-97 direct method to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex 1crystallographic data
Two triazole the manganese complex { [Mn (L) of oxygen ether of the present invention 2(N 3) 2] CHCl 3( 1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline, adopt " diffusion process ", i.e. L, Mn (ClO 4) 26H 2o and NaN 3at CHCl 3, CH 3filter after stirring half an hour in the mixed solvent of OH and water, filtrate normal temperature volatilizees two weeks to prepare this title complex
L。
The present invention's preferred example:
The preparation of 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L)
1-of the present invention (4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1, the preparation method of 2,4-triazole, its feature is adopting " one kettle way " at polar solvent, by 4,4 '-dibromodiphenyl ether, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are prepared in a heated condition; The wherein bromo-4-of 1-(4-bromine phenoxy group) benzene: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1;
4,4 '-dibromodiphenyl ether 1H-1,2,4-triazole
The present invention preferably 4,4 '-dibromodiphenyl ether: 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.In polar solvent, adopt " one kettle way ", by 4,4 '-dibromodiphenyl ether, 1H-1, this organic compound prepared in a heated condition by 2,4-triazole, salt of wormwood and cupric oxide;
Another preferred embodiment of the present invention
1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L) (0.1 mmol), Mn (ClO 4) 26H 2o (0.2 mmol) and NaN 3(0.2 mmol) is at CHCl 3(1 mL), CH 3filter after stirring half an hour in the mixed solvent of OH (4 mL) and water (6 mL), filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 25%.Ultimate analysis (C 33h 25cl 3mnN 18o 2) theoretical value (%): C, 44.62; H, 3.08; N, 18.36.Measured value: C, 44.715; H, 3.10; N, 18.44.
The present invention further discloses two triazole the manganese complex { [Mn (L) of oxygen ether 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) can be used as potential fluorescent material aspect and applied.
Two triazole the manganese complex { [Mn (L) of a kind of oxygen ether disclosed by the invention 2(N 3) 2] CHCl 3( 1) advantage and disadvantage that has of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) { [Mn (L) prepared by the present invention 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) production cost is low, method is easy, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1: title complex 1crystalline structure primitive figure;
Fig. 2: title complex 1one-dimensional catenary structure figure.
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 4,4 '-dibromodiphenyl ether, 1H-1,2,4-triazole, salt of wormwood and cupric oxide etc. all have commercially available.All raw materials are all buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.
Embodiment 1
4,4 '-dibromodiphenyl ether: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:10:30:1
CuO (0.5 mmol), salt of wormwood (15 mmol), 1H-1 is added respectively in 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 2,4-triazole (5 mmol), 4,4 '-dibromodiphenyl ether (1 mmol) and 20 mL DMF.Start and be stirred in 100 oc, reacts 24 hours.After reaction terminates, reaction solution is down to room temperature, filter, filtrate adds 100 mL water, separate out a large amount of precipitation, suction filtration, collect filter cake, 1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L).Yield 60%.
Embodiment 2
1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole (L) (0.1 mmol), Mn (ClO 4) 26H 2o (0.2 mmol) and NaN 3(0.2 mmol) is at CHCl 3(1 mL), CH 3filter after stirring half an hour in the mixed solvent of OH (4 mL) and water (6 mL), filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 25%.Ultimate analysis (C 33h 25cl 3mnN 18o 2) theoretical value (%): C, 44.62; H, 3.08; N, 18.36.Measured value: C, 44.715; H, 3.10; N, 18.44.
Embodiment 3
Crystal structure determination adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve crystalline structure from difference Fourier electron density map through least-squares refinement, 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 are in table 1.Structural motif is shown in Fig. 1, and one-dimensional catenary structure is shown in Fig. 2.
Table 1. title complex 1crystallographic data
Embodiment 4
The concrete instance that dyestuff or luminous agent use
Method: PARSTAT 2273 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 500 W xenon lamps 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 USB4000 plug-and-play Miniature optical linear light spectrometer.
Step: in order to definitely understand dyestuff at TiO 2adsorptive capacity on film, by dye sensitization TiO 2(geometric area is about 1 cm to nanometer crystal film 2) be immersed in 10 mL 0.01 molL -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 title complex is 5.9 × 10 -4mol/cm 2.
Result: compared with the methanol solution of dyestuff, 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 title complex 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 588 nm.
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 (4)

1. two triazole the manganese complex { [Mn (L) of oxygen ether 2(N 3) 2] CHCl 3( 1) structural motif, wherein L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole.
2. the monocrystalline of the two triazole manganese complex of oxygen ether described in claim 1, is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex 1crystallographic data
。
3. two triazole the manganese complex { [Mn (L) of oxygen ether described in claim 1 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) preparation method, it is characterized in that it be adopt " diffusion process ", i.e. L, Mn (ClO 4) 26H 2o and NaN 3at CHCl 3, CH 3filter after stirring half an hour in the mixed solvent of OH and water, filtrate normal temperature volatilizees two weeks to prepare this title complex
L。
4. two triazole the manganese complex { [Mn (L) of oxygen ether described in claim 1 2(N 3) 2] CHCl 3( 1) (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) as the application of potential fluorescent material aspect.
CN201510088007.8A 2015-02-26 2015-02-26 Oxygen ether double-triazole manganese complex with potential fluorescent material and preparation method thereof Pending CN104610368A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418689A (en) * 2016-01-05 2016-03-23 天津师范大学 2,5-dibromo-1,4-biphenoxyl diacetic acid cobalt acetate complex single crystal and application

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CN103772305A (en) * 2014-01-14 2014-05-07 天津师范大学 Oxyether triazole compound, and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN103772305A (en) * 2014-01-14 2014-05-07 天津师范大学 Oxyether triazole compound, and preparation method and application thereof

Non-Patent Citations (3)

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Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418689A (en) * 2016-01-05 2016-03-23 天津师范大学 2,5-dibromo-1,4-biphenoxyl diacetic acid cobalt acetate complex single crystal and application

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Application publication date: 20150513