CN104610344A - Oxygen ether bitriazol lead complex with potential fluorescent material and preparation method of complex - Google Patents
Oxygen ether bitriazol lead complex with potential fluorescent material and preparation method of complex Download PDFInfo
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- CN104610344A CN104610344A CN201510088235.5A CN201510088235A CN104610344A CN 104610344 A CN104610344 A CN 104610344A CN 201510088235 A CN201510088235 A CN 201510088235A CN 104610344 A CN104610344 A CN 104610344A
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- triazole
- oxygen ether
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Abstract
The invention discloses an oxygen ether bitriazol lead complex with a potential fluorescent material and a preparation method of the complex. The structure units of the oxygen ether bitriazol lead complex [Pb(L)(NO3)2] (1) are shown in a figure 1. Meanwhile, the invention also discloses a method for preparing [Pb(L)(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl)phenoxy)phenyl)-1H-1,2,4-triazole). A solvothermal method is adopted, namely the method comprises the following steps: reacting Pb(NO3)2, L, CHCl3, CH3OH and H2O at the temperature of 90 DEG C for three days, and slowly cooling to room temperature, thereby obtaining yellow bulk crystals suitable for X-ray single crystal diffraction. The invention further discloses an application of the oxygen ether bitriazol lead complex [Pb(L)(NO3)2] (1) (L=1-(4-(4-(1H-1,2,4-triazole-1-yl)phenoxy)phenyl)-1H-1,2,4-triazole) in the potential fluorescent material aspect.
Description
The present invention obtains state natural sciences fund general project (21471113), young top-notch personnel's support plan, Tianjin Education Commission general project (20140506), Tianjin Normal University Middl-age and youth faculty Academic innovations advance planning item (52XC1401), the subsidy of Tianjin State Scientific and Technological Commission general project (11JCYBJC03600) and Tianjin innovation team of institution of higher education training plan (TD12-5038).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to and state two triazole lead source [Pb (the L) (NO of oxygen ether
3)
2] (
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 " solvent-thermal method ", i.e. Pb (NO
3)
2, L, CHCl
3, CH
3oH and H
2o is 90
ounder C, yellow bulk crystals [Pb (the L) (NO that room temperature obtains applicable X-ray single crystal diffraction is slowly down in reaction for three days afterwards
3)
2] (
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 lead source [Pb (L) (NO
3)
2] (
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 lead source [Pb (the L) (NO of oxygen ether
3)
2] (
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 lead source [Pb (the L) (NO of oxygen ether
3)
2] (
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 lead source [Pb (the L) (NO of oxygen ether of the present invention
3)
2] (
1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole) monocrystalline, its feature is at employing " solvent-thermal method ", i.e. Pb (NO
3)
2, L, CHCl
3, CH
3oH and H
2o is 90
ounder C, reaction is slowly down to room temperature for three days afterwards 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)
Adopt " 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), Pb (NO
3)
2(0.2 mmo), CHCl
3(1 mL), CH
3oH (8 mL) and H
2o (1 mL), is put in 23 mL water heating kettles.90
oc heats and is slowly down to room temperature afterwards in three days, obtains the yellow bulk crystals of applicable X-ray single crystal diffraction after driving still.Productive rate: 20%.Ultimate analysis (C
32h
24n
16o
14pb
2) theoretical value (%): C, 30.24; H, 1.90; N, 17.63.Measured value: C, 30.22; H, 1.92; N, 17.69.
The present invention further discloses two triazole lead source [Pb (the L) (NO of oxygen ether
3)
2] (
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 lead source [Pb (the L) (NO of a kind of oxygen ether disclosed by the invention
3)
2] (
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) [Pb (the L) (NO prepared by the present invention
3)
2] (
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
1tomograph.
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), Pb (NO
3)
2(0.2 mmo), CHCl
3(1 mL), CH
3oH (8 mL) and H
2o (1 mL), is put in 23 mL water heating kettles.90
oc heats and is slowly down to room temperature afterwards in three days, obtains the yellow bulk crystals of applicable X-ray single crystal diffraction after driving still.Productive rate: 20%.Ultimate analysis (C
32h
24n
16o
14pb
2) theoretical value (%): C, 30.24; H, 1.90; N, 17.63.Measured value: C, 30.22; H, 1.92; N, 17.69.
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 three-dimensional 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 5.6 × 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 585 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 lead source [Pb (the L) (NO of oxygen ether
3)
2] (
1) structural motif as shown in Figure 1:
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 lead source 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 lead source [Pb (the L) (NO of oxygen ether described in claim 1
3)
2] (
1) preparation method of (L=1-(4-(4-(1H-1,2,4-triazole-1-base) phenoxy group) phenyl)-1H-1,2,4-triazole), it is characterized in that it adopts " solvent-thermal method ", i.e. Pb (NO
3)
2, L, CHCl
3, CH
3oH and H
2o is 90
ounder C, reaction is slowly down to room temperature for three days afterwards to prepare this title complex
L。
4. two triazole lead source [Pb (the L) (NO of oxygen ether described in claim 1
3)
2] (
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.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011889A (en) * | 2017-04-13 | 2017-08-04 | 桂林理工大学 | A kind of (double (4 carboxybenzyl) amino of N, N ') toluene lead source of novel fluorescent material 4 and synthetic method |
Citations (1)
| 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 |
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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 (1)
| Title |
|---|
| SHAO-BIN MIAO ET AL，: "Synthesis, Crystal Structure, and Properties of a 3D Cu(I) Coordination Polymer Based on Cu3(CN)2 Clusters and 1,3-Di-(1,2,4-Triazole-4-yl) Benzene", 《J CLUST SCI》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011889A (en) * | 2017-04-13 | 2017-08-04 | 桂林理工大学 | A kind of (double (4 carboxybenzyl) amino of N, N ') toluene lead source of novel fluorescent material 4 and synthetic method |
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