CN104610344B - 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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- CN104610344B CN104610344B CN201510088235.5A CN201510088235A CN104610344B CN 104610344 B CN104610344 B CN 104610344B CN 201510088235 A CN201510088235 A CN 201510088235A CN 104610344 B CN104610344 B CN 104610344B
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- triazole
- oxygen ether
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- fluorescent material
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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, day
Education Commission of Jinshi City general project (20140506), Tianjin Normal University's Middl-age and youth faculty Academic innovations propulsion planning item
(52XC1401), Tianjin Municipal Commission of Science and Technology general project (11JCYBJC03600) and Tianjin innovation team of institution of higher education culture meter
Draw the subsidy of (TD12-5038).
Technical field
The invention belongs to organic and Inorganic synthese technical field, is related to state double triazole lead source [Pb (the L) (NO of oxygen ether3)2]
(1) the preparation side of (L=1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles)
Method and the application as potential fluorescent material.
Background technology
1,2,4- triazole and its derivant have the coordination feature of pyrazoles and imidazoles concurrently, are that the stronger bridging of coordination ability is matched somebody with somebody
Body, has synthesized at present and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound.These parts can be former with the nitrogen on 1,2
Son and metallic ion coordination formation N1, N2- bridging patterns, unsubstituted for 41,2,4- triazole derivatives can pass through 2,4
On nitrogen-atoms formed N2, N4- bridging patterns, this N2, N4- bridgings pattern with imidazoles in metalloenzyme N1, N3- bridging patterns
It is similar.For the specific use of triazole class compounds is also manifested by the design of molecular device, synthesis has different dimensions
Metal complex is to complete the vital step of device.
The present invention is employing " solvent-thermal method ", i.e. Pb (NO3)2、L、CHCl3、CH3OH and H2O is 90oReact three days under C
It is slowly dropped to room temperature afterwards to obtain being adapted to yellow bulk crystals [Pb (the L) (NO of X-ray single crystal diffraction3)2] (1) (L = 1-(4-
(4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles).The coordination compound is alternatively arranged as potentially
Fluorescent material aspect is applied.
The content of the invention
Further object is that providing a kind of oxygen ether double triazole lead source [Pb (L) (NO3)2] (1) (L =
1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) monocrystalline and preparation method thereof.
For this current inventor provides following technical scheme：
Double triazole lead source [Pb (the L) (NO of oxygen ether3)2] (1) (L=1- (4- (4- (1H-1,2,4- triazole -1-
Base) phenoxy group) phenyl) -1H-1,2,4- triazoles) structural motif it is as shown in Figure 1.
The present invention further discloses double triazole lead source [Pb (the L) (NO of oxygen ether3)2] (1) (L = 1-(4-(4-
(1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) monocrystalline, it is characterised in that the mono-crystalline structures
Using APEX II CCD single crystal diffractometers, it is incidence to use through graphite monochromatised Mok alpha rays (λ=0.71073)
Radiation, withω-2θScan mode collects point diffraction, and through least square refinement cell parameter is obtained, from difference Fourier electricity
Sub- density map solves single crystal data using SHELXL-97 direct methods：
The crystallographic data of the coordination compound 1 of table 1.
Double triazole lead source [Pb (the L) (NO of oxygen ether of the present invention3)2] (1) (L = 1-(4-(4-(1H-1,2,4-
Triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) monocrystalline preparation method, its feature adopt " solvent thermal
Method ", i.e. Pb (NO3)2、L、CHCl3、CH3OH and H2O is 90oIt is slowly dropped to room temperature to prepare the coordination compound after reacting three days under C
L。
A preferred example of the invention：
The preparation of 1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles (L)
" one kettle way " is adopted in polar solvent, by 4,4 '-dibromodiphenyl ether, 1H-1,2,4- triazoles, potassium carbonate and copper oxide
Prepare in a heated condition；The bromo- 4- of wherein 1- (4- bromobenzene epoxides) benzene：1H-1,2,4- triazoles：Potassium carbonate：Copper oxide mole
Than for 2:10:30:1；
4,4 '-dibromodiphenyl ether 1H-1,2,4- triazoles
Preferably 4,4 '-dibromodiphenyl ether of the invention：1H-1,2,4- triazoles：Potassium carbonate：The mol ratio of copper oxide is 2:10:
30:1；Reaction temperature 80-200 DEG C, response time 12-120 hour.In polar solvent, adopt " one kettle way ", by 4,4 '-two
Dibromodiphenyl ether, 1H-1,2,4- triazoles, potassium carbonate and copper oxide prepare in a heated condition the organic compound；
Presently preferred embodiment
1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles (L) (0.1
mmol)、Pb(NO3)2 (0.2 mmo)、CHCl3 (1 mL)、CH3OH (8 mL) and H2O (1 mL), is put into 23 mL water heating kettles
In.90oC is slowly dropped to room temperature after heating three days, opens the yellow bulk crystals for obtaining being adapted to X-ray single crystal diffraction after kettle.Produce
Rate：20%.Elementary analysiss (C32H24N16O14Pb2) 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 double triazole lead source [Pb (the L) (NO of oxygen ether3)2] (1) (L = 1-(4-(4-
(1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) can obtain as potential fluorescent material aspect
To apply.
A kind of double triazole lead source [Pb (the L) (NO of oxygen ether disclosed by the invention3)2] (1) (L = 1-(4-(4-(1H-
1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles) monocrystalline has the advantage that with feature and 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 invention3)2] (1) (L=1- (4- (4- (1H-1,2,4- triazole -1-
Base) phenoxy group) phenyl) -1H-1,2,4- triazoles) low production cost, method simplicity, suitable large-scale production.
Description of the drawings
Fig. 1：The crystal structure primitive figure of coordination compound 1；
Fig. 2：The tomograph of coordination compound 1.
Specific embodiment
With reference to embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it
The scope of the present invention is limited by any way.Raw materials used 4,4 '-dibromodiphenyl ether, 1H-1,2,4- triazoles, potassium carbonate and
Copper oxide etc. is commercially available.All raw materials are bought from chemical reagents corporation both domestic and external, not through continuing to purify
But directly use.
Embodiment 1
4,4 '-dibromodiphenyl ether：1H-1,2,4- triazoles：Potassium carbonate：The mol ratio of copper oxide is 2:10:30:1
CuO (0.5 is separately added in the 50 mL three neck round bottom flask equipped with magneton, reflux condenser and thermometer
Mmol), potassium carbonate (15 mmol), 1H-1,2,4- triazoles (5 mmol), 4,4 '-dibromodiphenyl ether (1 mmol) and 20
mL DMF.Stirring is started 100oC, reacts 24 hours.After reaction terminates, reactant liquor is down to into room temperature, is filtered, filtrate adds
100 mL water, separate out a large amount of precipitations, and sucking filtration collects filter cake 1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) benzene
Base) -1H-1,2,4- triazoles (L).Yield 60%.
Embodiment 2
1- (4- (4- (1H-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles (L) (0.1
mmol)、Pb(NO3)2 (0.2 mmo)、CHCl3 (1 mL)、CH3OH (8 mL) and H2O (1 mL), is put into 23 mL water heating kettles
In.90oC is slowly dropped to room temperature after heating three days, opens the yellow bulk crystals for obtaining being adapted to X-ray single crystal diffraction after kettle.Produce
Rate：20%.Elementary analysiss (C32H24N16O14Pb2) 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 diffractometers, using through graphite monochromatised Mok alpha ray (λ
=0.71073) it is incident radiation, withω-2θScan mode collects point diffraction, and through least square refinement structure cell ginseng is obtained
Number, crystal structure, and Jing Lorentz lorentzs and polarity effect amendment are solved from difference Fourier electron density map using software.It is all of
H atom is synthesized by difference Fourier and handled thinks that position calculation determines.Detailed axonometry data are shown in Table 1.Structural motif is shown in
Fig. 1, three dimensional structure is shown in Fig. 2.
The crystallographic data of the coordination compound 1 of table 1.
Embodiment 4
The concrete instance that dyestuff or luminous agent are used
Method：What differentiated pulse volt-ampere (DPV) the curve negotiating Princeton Applied Research Laboratory of dye solution was developed
The electrochemical workstations of PARSTAT 2273 are measured.The DPV tests of solution adopt three-electrode system, and glass-carbon electrode is working electrode,
Auxiliary electrode is platinum plate electrode, homemade Ag/AgNO3Electrode is reference electrode；Electrolyte is the acetonitrile of 0.1molL-1TBAP
Solution.Reversible point is reduced to as internal standard, obtaining the corrected value between test system and standard hydrogen electrode system with Oxidation of Ferrocene.
Photoelectric transformation efficiencies of monochromatic incident illumination photoelectric transformation efficiency (IPCE) the description DSCs under monochromatic light action, is to turn
Move on to the electron number of external circuit and the ratio of incident illumination subnumber.During measurement, using 500 W xenon lamps as light source, incident illumination is passed through
The multifunctional assembled grating spectrograph of WDS-5 types obtains the monochromatic light under different wave length λ；Monochromatic light exposure is in the light sun of battery
Pole, by Keithley2400 digital sourcemeters current value I is read.Monochromatic good fortune illumination is micro- by USB4000 plug-and-play
Type light spectral instrument is measured.
Step：In order to have any actual knowledge of dyestuff in TiO2Adsorbance on film, by dye sensitization TiO2Nanometer crystal film (geometric surface
Product is about 1 cm2) it is immersed in the molL of 10 mL 0.01-1Sodium hydroxide methanol solution in overnight, treat that dyestuff is desorbed completely
The absorbance of solution is determined afterwards.Being washed one's face and rinsed one's mouth according to absorbance and molar absorptivity can calculate dyestuff on unit area nanometer crystal film
Adsorbance.The adsorbance of the coordination compound is 5.6 × 10-4 mol/cm2。
As a result：Compared with the methanol solution of dyestuff, dyestuff is in TiO2Absorption spectrum on film substantially broadens and red shift.This
Show dye molecule in TiO2Define the J- aggregations of first and tail.Say from the operation principle of DSCs, the light that dye aggregation causes
Spectrum width and red shift are highly beneficial for widening for the photoelectric respone scope of dyestuff.But at the same time, dye aggregation is known from experience
Its electron injection efficiency is substantially reduced, so as to cause the degraded performance of DSCs.So, generally add in dye solution co-adsorption
Agent is suppressing the aggregation of dyestuff.The coordination compound is in methanol solution and its in TiO2The fluorometric investigation of the purple solution on membrane electrode is adopted
With 2.5 × 10-5The methanol solution of mol/L, maximum emission wavelength is located at 585 nm.
After the preferred embodiment for describing in detail, it is familiar with the skilled worker and is clearly understood that, without departing from above-mentioned
Various change and modification can be carried out under claim and spirit, all technical spirits according to the present invention are to above example institute
Any simple modification, equivalent variations and the modification made, belongs to the scope of technical solution of the present invention.And the present invention is not also illustrated
The restriction of example embodiment in book.
Claims (2)
1. the double triazole lead source monocrystalline of a kind of oxygen ether, it is characterised in that the mono-crystalline structures adopt APEX II CCD single crystal diffractions
Instrument, using through graphite monochromatised Mok alpha rays, λ=0.71073 is incident radiation, withω-2θScan mode is collected and spread out
Exit point, through least square refinement cell parameter is obtained, and monocrystalline number is solved using software from difference Fourier electron density map
According to：
The structure of the double triazole lead source monocrystalline of the oxygen ether is [Pb (L) (NO3)2]；Wherein L=1- (4- (4- (1H-1,2,4-
Triazole -1- bases) phenoxy group) phenyl) -1H-1,2,4- triazoles.
2. double applications of the triazole lead source monocrystalline in terms of as potential fluorescent material of oxygen ether described in claim 1.
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| Title |
|---|
| 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;Shao-Bin Miao et al，;《J Clust Sci》;20140202;第25卷;参见第1139页第2-3段 * |
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