CN105294743A - 4H sulfide double triazole terephthalic acid zinc complex single crystal and preparation method as well as application thereof - Google Patents
4H sulfide double triazole terephthalic acid zinc complex single crystal and preparation method as well as application thereof Download PDFInfo
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- CN105294743A CN105294743A CN201510872026.XA CN201510872026A CN105294743A CN 105294743 A CN105294743 A CN 105294743A CN 201510872026 A CN201510872026 A CN 201510872026A CN 105294743 A CN105294743 A CN 105294743A
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Abstract
The invention discloses a 4H sulfide double triazole terephthalic acid zinc complex single crystal and a preparation method as well as application thereof. The structure of the single crystal is [Zn(L) (tpa)].1.5DMF.H2O, wherein L is equal to di(4-(4H-1,2,4-triazole-4-radical)phenyl) sulphur; tpa is equal to terephthalic acid. Meanwhile the invention also discloses the preparation method of the single crystal. A normal temperature volatilization method is adopted, i.e., the L, the tpa and Zn(NO3)2.6H2O are stirred in a mixed solvent of water and DMF, and then are filtered in half an hour, and a purple bulk crystal suitable for X-ray single crystal diffraction is obtained after filtrate is volatilized for two weeks at normal temperature, wherein the mole ratio of the L : the tpa : the Zn(NO3)2.6H2O is 1:1:1. The invention further discloses the application of the 4H sulfide double triazole terephthalic acid zinc complex single crystal as a potential fluorescent material in detection of a dye or illuminating agent adsorbing capacity.
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 two triazole terephthalic acid Zn complex monocrystalline [Zn (L) (the tpa)] 1.5DMFH of 4H thioether
2the preparation method of O and the application as potential fluorescent material, wherein, L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur; Tpa=terephthalic acid.
Background technology
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention adopts normal temperature volatilization method, i.e. L, tpa, Zn (NO
3)
26H
2o filters stir half an hour in the mixed solvent of water and DMF after, and filtrate normal temperature obtains applicable X-ray single crystal diffraction purple bulk crystal structure after volatilizing two weeks is [Zn (L) (tpa)] 1.5DMFH
2o, wherein, L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur; Tpa=terephthalic acid.This title complex also can be used as potential fluorescent material aspect and is applied.
Summary of the invention
Current inventor provides following technical scheme for this reason:
A monocrystalline for the two triazole terephthalic acid Zn complex of 4H thioether, is characterized in that this single crystal structure adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with
ω-2
θ
Scan 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:
Its structure is as follows:
[Zn (L) (tpa)] 1.5DMFH
2o, wherein
L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur;
Tpa=terephthalic acid.
The present invention further discloses the preparation method of the two triazole terephthalic acid Zn complex monocrystalline of 4H thioether, it is characterized in that it adopts normal temperature volatilization method, by L, tpa, Zn (NO
3)
26H
2o filters stir half an hour in the mixed solvent of water and DMF after, and filtrate normal temperature obtains the purple bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:tpa:Zn (NO
3)
26H
2the mol ratio of O is 1:1:1;
The structure of the two triazole terephthalic acid Zn complex of 4H thioether is [Zn (L) (tpa)] 1.5DMFH
2o; Wherein L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur; Tpa=terephthalic acid;
Ltpa。
The present invention further discloses the two triazole terephthalic acid Zn complex monocrystalline of 4H thioether as the application of potential fluorescent material in the adsorptive capacity detecting dyestuff or luminous agent, and experimental result shows:
(1) complex monocrystal in embodiment 2 has good selectivity and susceptibility to dyestuff, and detectability reaches 0.1ppm.
(2) can detect the luminous agent of trace, detection limit reaches 4.5 μ g/L
(3) complex monocrystal that prepared by embodiment 2 is 1.6 × 10 for the adsorptive capacity of dyestuff
-3mol/cm
2.
The present invention's preferred example:
The preparation of two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur (L):
4-(4-aminobenzene-thio) 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-aminobenzene-thio) 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 violet solid, yield 85%
The two formyl hydrazine of 4-(4-aminobenzene-thio) aniline.
The mol ratio of the preferred 4-of the present invention (4-aminobenzene-thio) aniline and two formyl hydrazine is 1:4; Temperature of reaction 150 DEG C, 24 hours reaction times.Adopt " one kettle way ", 4-(4-aminobenzene-thio) aniline and two formyl hydrazine are prepared this organic compound in a heated condition.
Another preferred embodiment of the present invention
Two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur (L) (0.1mmol), terephthalic acid (tpa) (0.1mmol) and Zn (NO
3)
26H
2o (0.1mmol) filters stir half an hour in the mixed solvent of water (4mL) and DMF (6mL) after, and filtrate normal temperature obtains the purple bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C
28.5h
29n
7.5o
6.5sZn) theoretical value (%): C, 50.48; H, 4.31; N, 15.49.Measured value: C, 50.40; H, 4.37; N, 15.47.
The advantage and disadvantage that the two triazole terephthalic acid Zn complex monocrystalline of a kind of 4H thioether 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 terephthalic acid Zn complex monocrystalline of the 4H thioether 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: title complex
monocrystallinecrystalline structure figure;
Fig. 2: title complex
monocrystallinetwo-dimensional layered 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 all have commercially available.All raw materials are all buy from chemical reagents corporation both domestic and external, such as 4-(4-aminobenzene-thio) aniline, wait raw material through continuing to purify but directly using.
Embodiment 1
4-(4-aminobenzene-thio) 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-aminobenzene-thio) 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 violet solid, two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur (L), yield 85%.
The two formyl hydrazine of 4-(4-aminobenzene-thio) aniline
The mol ratio of the preferred 4-of the present invention (4-aminobenzene-thio) aniline and two formyl hydrazine is 1:4; Temperature of reaction 150 DEG C, 24 hours reaction times.Adopt " one kettle way ", 4-(4-aminobenzene-thio) aniline and two formyl hydrazine are prepared this organic compound in a heated condition.
Embodiment 2
Two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur (L) (0.1mmol), terephthalic acid (tpa) (0.1mmol) and Zn (NO
3)
26H
2o (0.1mmol) filters stir half an hour in the mixed solvent of water (4mL) and DMF (6mL) after, and filtrate normal temperature obtains the purple bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks.Productive rate: 40%.Ultimate analysis (C
28.5h
29n
7.5o
6.5sZn) theoretical value (%): C, 50.48; H, 4.31; N, 15.49.Measured value: C, 50.40; H, 4.37; N, 15.47.
Embodiment 3
Crystal structure determination adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (l=0.71073) be incident radiation, with
w-
2qscan 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:
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 550nm.
Embodiment 5
The two triazole terephthalic acid Zn complex monocrystalline of 4H thioether 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 320nm and 550nm.
Step: two for 4H thioether triazole terephthalic acid Zn complex 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 of this compound
λ ex=320nm, emission wavelength
λ ex=550nm.
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. a monocrystalline for the two triazole of 4H thioether and terephthalic acid Zn complex, is characterized in that this single crystal structure adopts APEXIICCD single crystal diffractometer, and using through graphite monochromatised Mok alpha-ray λ=0.71073 is 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:
Its structure is as follows:
[Zn (L) (tpa)] 1.5DMFH
2o, wherein
L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur;
Tpa=terephthalic acid.
2. the preparation method of the two triazole terephthalic acid Zn complex monocrystalline of 4H thioether described in claim 1, is characterized in that it adopts normal temperature volatilization method, by L, tpa, Zn (NO
3)
26H
2o filters stir half an hour in the mixed solvent of water and DMF after, and filtrate normal temperature obtains the purple bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein L:tpa:Zn (NO
3)
26H
2the mol ratio of O is 1:1:1;
The structure of the two triazole zinc terephthalic acid complex monocrystal of 4H thioether is [Zn (L) (tpa)] 3.25H
2o; Wherein L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur; Tpa=terephthalic acid;
Ltpa。
3. the two triazole terephthalic acid Zn complex monocrystalline of 4H thioether 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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| CN104370837A (en) * | 2014-11-10 | 2015-02-25 | 天津师范大学 | Thioether bitriazole compound as well as preparation method and application of thioether bitriazole compound |
| CN104610302A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Antharcycline bis-triazole terephthalic acid zinc complex with potential fluorescent material and preparation method of antharcycline bis-triazole terephthalic acid zinc complex |
| CN104610315A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Cadmium oxyether bistriazol isophthalate complex with potential fluorescent material and preparation method of complex |
| CN104610304A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether double-triazole zinc complex with potential fluorescent material and preparation method thereof |
-
2015
- 2015-12-03 CN CN201510872026.XA patent/CN105294743A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370837A (en) * | 2014-11-10 | 2015-02-25 | 天津师范大学 | Thioether bitriazole compound as well as preparation method and application of thioether bitriazole compound |
| CN104610302A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Antharcycline bis-triazole terephthalic acid zinc complex with potential fluorescent material and preparation method of antharcycline bis-triazole terephthalic acid zinc complex |
| CN104610315A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Cadmium oxyether bistriazol isophthalate complex with potential fluorescent material and preparation method of complex |
| CN104610304A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether double-triazole zinc complex with potential fluorescent material and preparation method thereof |
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