CN107626282A - Application of fluoboric acid Ag (I) complexs that 4 (oxadiazole of 5 methyl 1,3,4) pyridine ligands are constructed in dyestuff is adsorbed - Google Patents
Application of fluoboric acid Ag (I) complexs that 4 (oxadiazole of 5 methyl 1,3,4) pyridine ligands are constructed in dyestuff is adsorbed Download PDFInfo
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- CN107626282A CN107626282A CN201610574035.5A CN201610574035A CN107626282A CN 107626282 A CN107626282 A CN 107626282A CN 201610574035 A CN201610574035 A CN 201610574035A CN 107626282 A CN107626282 A CN 107626282A
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- oxadiazoles
- dyestuff
- pyridine
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- isophthalic acids
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Abstract
The present invention discloses the application of fluoboric acid Ag (I) complexs that 4 (oxadiazole of 5 methyl 1,3,4) pyridine ligands are constructed in dyestuff is adsorbed, and complex uses monovalence silver ion AgBF4As main body, with 4 (5 methyl 1,3,4 oxadiazoles) pyridine is as part, fluoboric acid Ag (I) complex of 4 (oxadiazole of 5 methyl 1,3, the 4) pyridine ligands of synthesis with two-dimensional structure, the complex shows the absorption property for a variety of dyestuffs, has application potential.
Description
Technical field
The invention belongs to organic synthesis and Organometallic Chemistry technical field, She is Ji the 4- with two-dimensional structure of oxadiazole
The synthesis of fluoboric acid-Ag (I) complex of (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand, in particular it is that there is two dimension
The synthesis of fluoboric acid-Ag (I) complex of 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand of structure and its method.
Background technology
Coordinative Chemistry is a science to grow up on the basis of inorganic chemistry, and the main object that it is studied is coordination
Compound (coordination compounds, abbreviation complex).From earlier 1900s late nineteenth century youth scholar
Since Werner proposes the theory foundation Coordinative Chemistry of often referred to as Werner coordination theory now, it is all the time in inorganization
Learn the forward position of research.Complex refer to self-existent stable compound further combined with atom or ion answering for being formed
Heterocompound.The research of molecular material is most noticeable a kind of advanced subject in recent years, in the world advanced American and Britain, moral, method
This research is included in respective high-tech development planning Deng state, nineteen ninety-five, molecular material was also defined as basic science by Japan
One of seven problems of pilot study and give emphasis subsidy.Molecular material refers to the three-dimensional material being assembled into by molecular cell,
The characteristics of in this structure, makes us possibly through the appropriate molecule of selection and different assembling modes to prepare with specific
The macroscopic material of functional character.This kind of complex has the characteristic of inorganic compound and organic compound concurrently, due to answering for its composition
Polygamy, the diversity of metal and ligand species, the adjustability of coordination environment, make in molecular material most potential application
A kind of system of prospect.Recent years abroad has collected the subject that such research is pupil's thing, material, chemistry intersect, referred to as metal
Complex material chemistry.In recent years, with the development of modern industry, anionic dye pollutant have become one it is more and more tighter
The environmental problem of weight, for example, it is Congo red etc., it always is chemists' focus of attention.Because these anionic pollutants can be right
Health and environment produce serious infringement, and being classified as by Environmental Protection Agency USA worldwide needs priority treatment
Environmental contaminants.Because these anionic dye pollutants have been widely used in metallurgy, pigment manufacture, leather tanning and timber
Deng field, the new material that preparation could capture and separate these anionic pollutants from industrial wastewater is very important.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide based on 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyrrole
Fluoboric acid-Ag (I) complexs and its synthetic method that pyridine part is constructed, using monovalence silver ion as main body, with 4- (5- first
Base -1,3,4- oxadiazoles) pyridine as part, match somebody with somebody by 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine that synthesis has two-dimensional structure
Fluoboric acid-Ag (I) complex of body.
The technical purpose of the present invention is achieved by following technical proposals：
Based on fluoboric acid-Ag (I) complex of 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand, chemical general formula is：
[Ag(L)2]·BF4
L is 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine, and as part, its structural formula is
There is the structure of a center silver (Ag1) in each complex molecule, for the basic of each complex molecule
In construction unit, ligand L bridging center Ag (I) ion ultimately forms the structure of two dimensional surface in complex, silver atoms Ag1 with
Four nitrogen-atoms form four-coordination AgN4Coordination configuration, two of which nitrogen-atoms come from part 4- (5- methyl isophthalic acids, 3,4- Evil bis-
Azoles) nitrogen-atoms in pyridine in pyridine ring (hexatomic ring), two nitrogen-atoms come from part 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyrrole
Nitrogen-atoms N3 in Ding Zhong oxadiazoles structures (five-membered ring), i.e., close to the nitrogen-atoms of methyl group in oxadiazoles structure.
The preparation method of above-mentioned complex, carry out as steps described below：
According to chemical general formula [Ag (L)2]·BF4Shown molar ratio weighs AgBF4With part 4- (5- methyl isophthalic acids, 3,4-
Oxadiazole) after pyridine is well mixed, reacts under 150-180 degrees Celsius, obtained after naturally cooling to 20-25 degrees Celsius of room temperature
Colourless transparent crystal, it is the complex of the present invention.
In above-mentioned preparation method, reaction temperature is 160-170 degrees Celsius, at least 12 hours reaction time, preferably 40-
72 hours.
In above-mentioned preparation method, AgBF is selected4It is dispersed in water, ligand 4- (5- methyl isophthalic acids, 3,4- Evil bis-
Azoles) pyridine is dispersed in ethanol, then water and ethanol are uniformly dispersed, and the volume of water and ethanol is (1-1.5)：2.
In above-mentioned preparation method, realized by mechanical agitation or ultrasound dispersed.
In above-mentioned preparation method, select to be reacted and be incubated in water heating kettle.
The application of complex dyestuff in absorption/removal water environment of the present invention, dyestuff are Congo red, methyl orange, lemon
It is yellow.
The complex of the present invention is uniformly mixed with the system already provided with dyestuff, and it is small to stand at least 12 at room temperature
When, preferably 12-48 hours.
The intensity before and after complex adsorption dyestuff is determined respectively using ultraviolet specrophotometer, to determine corresponding ripple
It is long：Congo red is 500nm, methyl orange 460nm, lemon yellow 428nm.
It is 0.4-0.6mol/mol for Congo red absorption/removal effect, for absorption/removal effect of methyl orange
For 12-13mg/mol, absorption/removal effect for lemon yellow is 12-12.5mg/mol.
The invention belongs to organic synthesis and Organometallic Chemistry technical field, there is provided based on 4- (5- methyl isophthalic acids, 3,4- Evil bis-
Azoles) fluoboric acid-Ag (I) complexs constructed of pyridine ligand and its synthetic method, there is provided there are 4- (5- methyl isophthalic acids, 3,4- Evil bis-
Azoles) fluoboric acid-Ag (I) complexs constructed of pyridine ligand and its synthetic method, the complex shown for a variety of dyestuffs
Absorption property, there is application potential.
Brief description of the drawings
Fig. 1 is the schematic arrangement of fluoboric acid-Ag (I) complex that the present invention synthesizes.
Fig. 2 is that the ultraviolet spectra before and after adsorbing Congo red 12 hours is carried out using the complex of the present invention.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.The medicine that following embodiments use is from hundred
Ling Wei Reagent Companies buy, and rank is analysis pure rank (AgBF4,4- pyridine carboxylic acid hydrazide, triethly orthoacetate, ether, the Congo
It is red, methyl orange, lemon yellow).Experimental implementation uses Schlenk technologies, and solvent purifies by normal process.Fusing point passes through
Boetius block apparatus determines.1H H NMR spectroscopies are recorded by mercury variable V x300 spectrophotometers, surveying range：300MHz.Chemistry
Displacement, δ, determined with reference to the TMS of international standard.
Embodiment 1：Synthesize 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine (i.e. ligand L)
The structural formula (i.e. L structural formula) of 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand is
L preparation method:35mmol 4- pyridine carboxylic acid hydrazides are put into 95mmol (2.7 equivalent) triethly orthoacetate, are returned
Stream 12 hours, is filtered after being cooled to room temperature, is washed twice using 15mL ether, is dried in vacuo, has been obtained the part of white needles
L.Prepare document:J.Org.Chem.1953,18,1368.
Embodiment 2：Fluoboric acid-Ag (I) complex that pyridine synthesis part is constructed
Weigh 0.0973g (0.5mmol) AgBF4Dissolved with 5mL water, weigh ligand L 0.162g (1mmol) 10mL second
Alcohol is dissolved, and both the above solution is mixed, and is then put into 15mL water heating kettle and is kept for three days that (daily 24 is small at 160 DEG C
When), colourless transparent crystal is obtained after slow cooling (naturally cooling to 20-25 degrees Celsius of room temperature).
Embodiment 3：The measure of complex
(1) single crystal diffraction
Selection size is that 0.25mm × 0.22mm × 0.2mm monocrystalline is spread out with BRUKER SMART 1000X- ray single crystals
Instrument is penetrated, diffraction light sources are used as using the MoK α radiation (λ=0.071 073nm) of graphite monochromator, at a temperature of 296 (2) K, withScan mode, in the range of 3.559 °≤θ≤24.998 °, 4096 point diffractions is collected altogether, wherein 1685 are independently spread out
Exit point.Crystal structure is solved by direct method, non-hydrogen atom is obtained by difference Fourier synthetic method, it is determined that and amendment hydrogen atom
Method is theoretical hydrogenation, isotropism and anisotropy thermal parameter is respectively adopted to hydrogen atom and non-hydrogen atom structure is carried out entirely
Matrix least square method amendment, all calculate and completed with SHELXS-97 and SHELXL-97 program bags.The predominant crystal of complex
Data are learned to be listed in the table below.
The monocrystalline data of complex
(2) crystal structure
As shown in Figure 1, the crystal category monoclinic system of complex, I2/ a space groups, complex [Ag (L) of the present invention2·
BF4] main bond distance and bond angle it is as shown in the table.There is the structure of a center silver (Ag1) in each complex molecule, it is right
In the basic structural unit of each complex molecule, ligand L bridging center Ag (I) ion ultimately forms two dimension in complex
The structure of plane, silver atoms Ag1 and four nitrogen-atoms form four-coordination AgN4Coordination configuration, two of which nitrogen-atoms carry out autogamy
Nitrogen-atoms in body 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine in pyridine ring (hexatomic ring), two nitrogen-atoms come from part 4-
Nitrogen-atoms N3 in (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine Zhong oxadiazoles structure (five-membered ring), i.e., lean in oxadiazoles structure
The nitrogen-atoms of nearly methyl group.
The part bond distance of complex 1 and bond angle
Embodiment 4：The processing of pollutant in water environment
(1) it is used as congo red sorbing material
By ultraviolet specrophotometer, respectively to determining Congo red UV absorption intensity before and after complex adsorption, it is determined that
To Congo red adsorption effect.The complex l (0.1mmol) of preparation is taken to be placed on Congo red (0.01molL-1, 0.1mmol)
In the aqueous solution (10mL).Rock corresponding mixture and be placed on 20-25 degrees Celsius of room temperature lower 12 hours, adsorption process is by ultraviolet
Visible spectrum is tested, Congo red to have obvious absorption respectively in 500nm, in the range of different time intervals, uses pipettor
0.1mL solution is drawn, the UV, visible light peak intensity of corresponding solution is measured after being diluted to 2mL with deionized water.For unadsorbed
The concentration of anionic pollutant can be calculated by below equation：
Wherein D is complex 1 for Congo red adsorption rate, C0, A0And C1, A1Before being absorption respectively and after absorption
Congo red concentration in aqueous and absorbance.As a result：The suction that complex 1 has had to the congo red in the aqueous solution
Attached/to remove effect, the color of the aqueous solution is changed into almost colourless from clarification shiny red in adsorption process, has indicated congo red
Through being effectively adsorbed onto in two-dimentional Ag (I) complex, adsorption rate is 0.47mol/mol (for Congo Red), as shown in Figure 2.
Repeatedly test is average up to 0.4-0.6mol/mol.
(2) it is directed to the absorption of methyl orange dye
By ultraviolet specrophotometer, the UV absorption before and after methyl orange is adsorbed to complexes measuring in aqueous respectively
Intensity, it is determined that to Adsorption of Methyl Orange effect.The complex 1 (0.1mmol) of preparation is taken to be placed on methyl orange (0.01molL-1,
In the aqueous solution (10mL) 0.1mmol).Rock corresponding mixture and be placed on 20-25 degrees Celsius of room temperature lower 48 hours, adsorb
Process is tested by uv-vis spectra, and methyl orange has obvious absorption respectively in 460nm, in different time interval scopes
It is interior, 0.1mL solution is drawn with pipettor, the UV, visible light peak intensity of corresponding solution is measured after being diluted to 2mL with deionized water.
It can be calculated for the concentration of unadsorbed anionic pollutant by below equation：
Wherein D is adsorption rate of the complex 1 for methyl orange, C0, A0And C1, A1Before being absorption respectively and after absorption
Methyl orange concentration and absorbance in aqueous.As a result：Complex 1 has certain suction to the methyl orange dye in the aqueous solution
Attached/to remove effect, adsorption rate 12.68mg/mol, repeatedly test is average up to 12-13mg/mol.
(3) it is directed to the absorption of lemon yellow dye
By ultraviolet specrophotometer, the UV absorption before and after lemon yellow is adsorbed to complexes measuring in aqueous respectively
Intensity, it is determined that to lemon yellow adsorption effect.The complex 1 (0.1mmol) of preparation is taken to be placed on lemon yellow (0.01molL-1,
In the aqueous solution (10mL) 0.1mmol).Rock corresponding mixture and be placed on 20-25 degrees Celsius of room temperature lower 48 hours, adsorb
Process is tested by uv-vis spectra, and lemon yellow has obvious absorption respectively in 428nm, in different time interval scopes
It is interior, 0.1mL solution is drawn with pipettor, the UV, visible light peak intensity of corresponding solution is measured after being diluted to 2mL with deionized water.
It can be calculated for the concentration of unadsorbed anionic pollutant by below equation：
Wherein D is adsorption rate of the complex 1 for lemon yellow, C0, A0And C1, A1Before being absorption respectively and after absorption
Lemon yellow concentration and absorbance in aqueous.As a result：Complex 1 has absorption/shifting to the lemon yellow dye in the aqueous solution
Except effect, adsorption rate 12.39mg/mol, repeatedly test is average up to 12-12.5mg/mol.
On subsidizing the statement of research or development：The present invention is in Tianjin application foundation and cutting edge technology research plan day
Jinshi City's Nsfc Projects (Grant no.14JCQNJC05900) and project of national nature science fund project (Grant
No.21301128 carried out under subsidy).
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal
Fall into protection scope of the present invention.
Claims (6)
- Fluoboric acid-Ag (I) complexs that 1.4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand is constructed answering in dyestuff is adsorbed It is with, it is characterised in that coordination chemistry formula：[Ag(L)2]·BF4, L is 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine, is made For part, its structural formula isOccurs the structure of a center silver in each complex molecule, for the basic structural unit of each complex molecule In, ligand L bridging center Ag (I) ion ultimately forms the structure of two dimensional surface, silver atoms and four nitrogen-atoms in complex Form four-coordination AgN4Coordination configuration, two of which nitrogen-atoms are come from part 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine Pyridine ring nitrogen, two nitrogen-atoms are come from part 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine in oxadiazole structure Nitrogen-atoms N3, i.e., in oxadiazoles structure close to methyl group nitrogen-atoms.
- 2. fluoboric acid-the Ag (I) that 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand according to claim 1 is constructed matches somebody with somebody Application of the compound in dyestuff is adsorbed, it is characterised in that the bond distance of complex and bond angle are as shown in the table
- 3. fluoboric acid-the Ag (I) that 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand as claimed in claim 1 is constructed coordinates Application of the thing in dyestuff is adsorbed, it is characterised in that complex is uniformly mixed with the system already provided with dyestuff, and in room temperature It is lower to stand at least 12 hours, preferably 12-48 hours.
- 4. fluoboric acid-the Ag (I) that 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand as claimed in claim 1 is constructed coordinates Application of the thing in dyestuff is adsorbed, it is characterised in that dyestuff is Congo red, methyl orange, lemon yellow.
- 5. fluoboric acid-the Ag (I) that 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand as claimed in claim 4 is constructed coordinates Application of the thing in dyestuff is adsorbed, it is characterised in that using ultraviolet specrophotometer respectively to complex adsorption dyestuff before and after Intensity is determined, to determine corresponding wavelength：Congo red is 500nm, methyl orange 460nm, lemon yellow 428nm.
- 6. fluoboric acid-the Ag (I) that 4- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand as claimed in claim 4 is constructed coordinates Application of the thing in dyestuff is adsorbed, it is characterised in that for Congo red absorption/removal effect it is 0.4-0.6mol/mol, pin Absorption/removal effect to methyl orange is 12-13mg/mol, and absorption/removal effect for lemon yellow is 12-12.5mg/ mol。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997386A (en) * | 2018-05-25 | 2018-12-14 | 安徽理工大学 | A kind of zinc metal organic complex and preparation method thereof that double ligands are constructed |
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| CN101024200A (en) * | 2006-02-22 | 2007-08-29 | 兰爱克谢丝德国有限责任公司 | Novel catalyst systems and their use for metathesis reactions |
| CN104768961A (en) * | 2012-10-29 | 2015-07-08 | 优美科股份公司及两合公司 | Ruthenium-based metathesis catalysts, precursors for their preparation and their use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108997386A (en) * | 2018-05-25 | 2018-12-14 | 安徽理工大学 | A kind of zinc metal organic complex and preparation method thereof that double ligands are constructed |
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