CN107661746A - Hexafluorophosphoric acid Ag (I) complexs and its synthetic method constructed based on 3 (oxadiazole of 5 methyl 1,3,4) pyridine ligands - Google Patents
Hexafluorophosphoric acid Ag (I) complexs and its synthetic method constructed based on 3 (oxadiazole of 5 methyl 1,3,4) pyridine ligands Download PDFInfo
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- CN107661746A CN107661746A CN201610623608.9A CN201610623608A CN107661746A CN 107661746 A CN107661746 A CN 107661746A CN 201610623608 A CN201610623608 A CN 201610623608A CN 107661746 A CN107661746 A CN 107661746A
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 81
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003446 ligand Substances 0.000 title claims abstract description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 13
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 title abstract 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 229910017744 AgPF6 Inorganic materials 0.000 claims abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 abstract description 17
- 235000005979 Citrus limon Nutrition 0.000 abstract description 13
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 13
- 229940012189 methyl orange Drugs 0.000 abstract description 13
- 244000248349 Citrus limon Species 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 150000003222 pyridines Chemical class 0.000 abstract description 2
- ZMSIFDIKIXVLDF-UHFFFAOYSA-N 2-methyl-1,3,4-oxadiazole Chemical class CC1=NN=CO1 ZMSIFDIKIXVLDF-UHFFFAOYSA-N 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000003851 azoles Chemical group 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 239000001048 orange dye Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010181 polygamy Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 210000001747 pupil Anatomy 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/10—Silver compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses based on 3 (5 methyl 1,3,4 oxadiazoles) hexafluorophosphoric acid Ag (I) complexs constructed of pyridine ligand and its synthetic method, for in the basic structural unit of each complex molecule, ligand L forms one-dimensional duplex structure, two PF by nitrogen-atoms bridging center silver ion in complex6For free state, Ag (I) while in the presence of two kinds of coordination situations.According to chemical general formula { [Ag2(L)3]·2PF6Shown in molar ratio weigh AgPF6After being well mixed with 3 (oxadiazole of 5 methyl 1,3,4) pyridines, reacted under 150-180 degrees Celsius, colourless transparent crystal is obtained after naturally cooling to 20-25 degrees Celsius of room temperature, be the complex of the present invention.The complex of the present invention has the effect of absorption/removal to Congo red, methyl orange, lemon yellow in water environment.
Description
Technical field
The invention belongs to organic synthesis and Organometallic Chemistry technical field, She is Ji oxadiazole has one-dimensional duplex structure
3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand hexafluorophosphoric acid-Ag (I) complex synthesis, in particular be tool
There are hexafluorophosphoric acid-Ag (I) complexs and its synthesis of 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand of one-dimensional duplex structure
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 existing deficiency, there is provided have one-dimensional duplex structure based on 3- (5- methyl isophthalic acids, 3,
4- Evil diazole) hexafluorophosphoric acid-Ag (I) complexs constructed of pyridine ligand and its synthetic method, using monovalence silver ion as leading
Body, with 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridines as part, synthesis with one-dimensional duplex structure 3- (5- methyl isophthalic acids, 3,
4- oxadiazoles) pyridine ligand hexafluorophosphoric acid-Ag (I) complex.
The technical purpose of the present invention is achieved by following technical proposals：
Hexafluorophosphoric acid-Ag (I) complex constructed based on 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand, chemistry are logical
Formula is：{[Ag2(L)3]·2PF6}；
L is 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine, and as part, its structural formula is
For in the basic structural unit of each complex molecule, ligand L passes through nitrogen-atoms bridging center silver in complex
Ion forms one-dimensional duplex structure, two PF6For free state, Ag (I) while in the presence of two kinds of coordination situations：
The first coordination situation：Silver atoms Ag1 and four nitrogen-atoms are coordinated to form AgN4Coordination configuration, two nitrogen-atoms come
From in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings (i.e. five-membered ring in ligand molecular) with methyl group phase
Ortho position the nitrogen-atoms N2 and N4A of carbon atom even, a nitrogen-atoms come from 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules
The meta nitrogen-atoms N8 for the carbon atom being connected in oxadiazole rings (i.e. five-membered ring in ligand molecular) with methyl group, a nitrogen original
Son comes from the nitrogen-atoms in pyridine ring (i.e. hexatomic ring in ligand molecular) in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules
N3A；
Second of coordination situation：Silver atoms Ag2 and four nitrogen-atoms are coordinated to form AgN4Coordination configuration, a nitrogen-atoms come
From in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings (i.e. five-membered ring in ligand molecular) with methyl group phase
The ortho position nitrogen-atoms N7 of carbon atom even, a nitrogen-atoms come from 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules Evil bis-
The meta nitrogen-atoms N1 for the carbon atom being connected in azoles ring (i.e. five-membered ring in ligand molecular) with methyl group, two nitrogen-atoms come from
Nitrogen-atoms N6 and N9A in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules in pyridine ring (i.e. hexatomic ring in ligand molecular).
The preparation method of above-mentioned complex, carry out as steps described below：
According to chemical general formula { [Ag2(L)3]·2PF6Shown in molar ratio weigh AgPF6With 3- (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, AgPF is selected6It is dispersed in water, part 3- (5- methyl isophthalic acids, 3,4- oxadiazoles)
Pyridine is dispersed in ethanol, then water and ethanol are uniformly dispersed, and the volume ratio 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 48-72 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 0.38-0.43mol/mol for Congo red absorption/removal effect, absorption/removal for methyl orange is imitated
Fruit is 11.8-12.4mg/mol, and absorption/removal effect for lemon yellow is 12.2-12.5mg/mol.
The invention belongs to organic synthesis and Organometallic Chemistry technical field, there is provided have the 3- (5- of one-dimensional duplex structure
Methyl isophthalic acid, 3,4- oxadiazoles) pyridine ligand hexafluorophosphoric acid-Ag (I) complexs and its synthetic method, the complex show pin
To the absorption property of a variety of dyestuffs, there is application potential.
Brief description of the drawings
Fig. 1 is the { [Ag that the present invention synthesizes2(L)3]·2PF6Complex molecular structure；
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
With reference to specific embodiment the present invention is further described technical scheme.What following embodiments used
Medicine is bought from lark prestige Reagent Company, and rank is the pure rank (AgPF of analysis6, Niacin Nicitinic Acid hydrazides, triethly orthoacetate,
Ether, Congo red, ethanol, methyl orange, lemon yellow).Experimental implementation uses Schlenk technologies, and solvent purifies by normal process.
Fusing point is determined by Boetius block apparatus.1H H NMR spectroscopies are recorded by mercury variable V x300 spectrophotometers, surveying range：
300MHz.Chemical shift, δ, determined with reference to the TMS of international standard.
Embodiment 1：Synthesize 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine (i.e. ligand L)
The structural formula (i.e. L structural formula) of 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand is
L preparation method:35mmol Niacin Nicitinic Acid hydrazides is put into 95mmol (2.7 equivalent) triethly orthoacetate, is 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, preparation method and process parameters document:J.Org.Chem.1953,18,1368.
Embodiment 2：Hexafluorophosphoric acid-Ag (I) complex that pyridine synthesis part is constructed
Weigh 0.2528g (1mmol) AgPF6, dissolved with 5mL water, weigh ligand L 0.2416g (1.5mmol) and use 10mL
Ethanol 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) according to Ag2P2O3N9F12C24H21The theoretical value (%) of calculating：C, 29.144%；H, 2.14%；N, 12.74%；
Elementary analysis result, experiment value (%)：C, 29.9%；H, 2.35%；N, 12.79%.Illustrate that element composition is basic in complex
It is consistent with theoretical calculation.
(2) single crystal diffraction
Selection size is that 0.22mm × 0.20mm × 0.17mm 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 1.085 °≤θ≤28.417 °, 12765 point diffractions is collected altogether, wherein 8421 are independently spread out
Exit point [σ of I ＞ 2 (I)] (Rint=0.0218).Crystal structure is solved by direct method, and non-hydrogen atom is by difference Fourier synthetic method
Obtain, it is determined that and the method for amendment hydrogen atom is theoretical hydrogenation, hydrogen atom and non-hydrogen atom are respectively adopted isotropism and each
Anisotropy thermal parameter carries out complete matrix least square method amendment to structure, all calculates and uses SHELXS-97 and SHELXL-97 programs
Bag is completed.The predominant crystal data of complex is listed in the table below.
The monocrystalline data of complex
(3) crystal structure
As shown in Figure 1, the crystal category anorthic system of complex, P-1 space groups, occur simultaneously in each complex molecule
The structure of two center silver (Ag1 and Ag2), complex { [Ag of the present invention2(L)3]·2PF6Main bond distance and bond angle it is as follows
Shown in table.For the basic structural unit of complex, ligand L forms one by nitrogen-atoms bridging center silver ion in complex
Tie up duplex structure, two PF6For free state, Ag (I) while in the presence of two kinds of coordination situations：
The first coordination situation：Silver atoms Ag1 and four nitrogen-atoms are coordinated to form AgN4Coordination configuration, two nitrogen-atoms come
From in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings (i.e. five-membered ring in ligand molecular) with methyl group phase
Ortho position the nitrogen-atoms N2 and N4A of carbon atom even, a nitrogen-atoms come from 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules
The meta nitrogen-atoms N8 for the carbon atom being connected in oxadiazole rings (i.e. five-membered ring in ligand molecular) with methyl group, a nitrogen-atoms
Nitrogen-atoms N3A in pyridine ring (i.e. hexatomic ring in ligand molecular) in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules；
Second of coordination situation：Silver atoms Ag2 and four nitrogen-atoms are coordinated to form AgN4Coordination configuration, a nitrogen-atoms come
From in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings (i.e. five-membered ring in ligand molecular) with methyl group phase
The ortho position nitrogen-atoms N7 of carbon atom even, a nitrogen-atoms come from 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules Evil bis-
The meta nitrogen-atoms N1 for the carbon atom being connected in azoles ring (i.e. five-membered ring in ligand molecular) with methyl group, two nitrogen-atoms come from
Nitrogen-atoms N6 and N9A in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules in pyridine ring (i.e. hexatomic ring in ligand molecular).
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 by it is ultraviolet can
See spectrum test, it is Congo red that there is obvious absorption respectively in 500nm, in the range of different time intervals, inhaled with pipettor
0.1mL solution is taken, 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 becomes colorless from clarification shiny red in adsorption process, indicate congo red by
Effectively it is adsorbed onto in one-dimensional double-strand Ag (I) complex.Adsorption rate is 0.41mol/mol (for Congo Red), as shown in Figure 2.
Repeatedly test is average up to 0.38-0.43mol/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, adsorbed
Journey is tested by uv-vis spectra, and methyl orange has obvious absorption respectively in 460nm, in the range of different time intervals,
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 is right
It can be calculated in 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
It is attached/to remove effect, adsorption rate 12.11mg/mol.Repeatedly test is average up to 11.8-12.4mg/mol.
(3) it is directed to the absorption of lemon yellow dye
By ultraviolet specrophotometer, the ultraviolet suction before and after lemon yellow is adsorbed to the compound determination in aqueous respectively
Intensity is received, 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, adsorbed
Journey is tested by uv-vis spectra, and lemon yellow has obvious absorption respectively in 428nm, in the range of different time intervals,
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 is right
It can be calculated in 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 certain suction to the lemon yellow dye in the aqueous solution
It is attached/to remove effect, adsorption rate 12.23mg/mol.Repeatedly test is average up to 12.2-12.5mg/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 (9)
1. hexafluorophosphoric acid-Ag (I) complex constructed based on 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand, its feature are existed
In chemical general formula is：{[Ag2(L)3]·2PF6}；
L is 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine, and as part, its structural formula is
For in the basic structural unit of each complex molecule, ligand L passes through nitrogen-atoms bridging center silver ion in complex
Form one-dimensional duplex structure, two PF6For free state, Ag (I) while in the presence of two kinds of coordination situations：
The first coordination situation：Silver atoms Ag1 and four nitrogen-atoms are coordinated to form AgN4Coordination configuration, two nitrogen-atoms come from 3-
The ortho position nitrogen-atoms N2 for the carbon atom being connected in (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings with methyl group
And N4A, a nitrogen-atoms is come from 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings to be connected with methyl group
Carbon atom meta nitrogen-atoms N8, a nitrogen-atoms comes from pyridine ring in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules
In nitrogen-atoms N3A；
Second of coordination situation：Silver atoms Ag2 and four nitrogen-atoms are coordinated to form AgN4Coordination configuration, a nitrogen-atoms come from 3-
The ortho position nitrogen-atoms for the carbon atom being connected in (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings with methyl group
N7, a nitrogen-atoms come from what is be connected in 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules oxadiazole rings with methyl group
The meta nitrogen-atoms N1 of carbon atom, two nitrogen-atoms are come from 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) Pyridine Molecules in pyridine ring
Nitrogen-atoms N6 and N9A.
2. hexafluorophosphoric acid-the Ag according to claim 1 constructed based on 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine ligand
(I) complex, it is characterised in that complex { [Ag2(L)3]·2PF6Bond distance and bond angle it is as shown in the table：
3. the preparation method of complex as claimed in claim 1, it is characterised in that carry out as steps described below：According to chemistry
Formula { [Ag2(L)3]·2PF6Shown in molar ratio weigh AgPF6Mixed with 3- (5- methyl isophthalic acids, 3,4- oxadiazoles) pyridine
After uniformly, reacted under 150-180 degrees Celsius, obtain colourless transparent crystal after naturally cooling to 20-25 degrees Celsius of room temperature, i.e.,
For the complex of the present invention.
4. preparation method according to claim 3, it is characterised in that reaction temperature is 160-170 degrees Celsius.
5. preparation method according to claim 3, it is characterised in that at least 12 hours reaction time.
6. preparation method according to claim 3, it is characterised in that preferably 40-72 hours.
7. preparation method according to claim 3, it is characterised in that selection AgPF6It is dispersed in water, part 3- (5-
Methyl isophthalic acid, 3,4- oxadiazoles) pyridine is dispersed in ethanol, then water and ethanol are uniformly dispersed, the volume ratio of water and ethanol
For (1-1.5)：2.
8. preparation method according to claim 7, it is characterised in that realized by mechanical agitation or ultrasound and uniformly divided
Dissipate.
9. preparation method according to claim 3, it is characterised in that selection is reacted and protected in water heating kettle
Temperature.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693727A (en) * | 2009-10-22 | 2010-04-14 | 复旦大学 | Tetranuclear/hexanuclear macrocycle compound containing iridium, rhodium and ruthenium with half-sandwich structure and preparation method thereof |
| CN104844633A (en) * | 2015-04-27 | 2015-08-19 | 天津师范大学 | High-temperature solvothermal synthesis and application of tetranuclear Ag(I) cluster based on methylpyridine-triazole |
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2016
- 2016-07-28 CN CN201610623608.9A patent/CN107661746A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693727A (en) * | 2009-10-22 | 2010-04-14 | 复旦大学 | Tetranuclear/hexanuclear macrocycle compound containing iridium, rhodium and ruthenium with half-sandwich structure and preparation method thereof |
| CN104844633A (en) * | 2015-04-27 | 2015-08-19 | 天津师范大学 | High-temperature solvothermal synthesis and application of tetranuclear Ag(I) cluster based on methylpyridine-triazole |
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| BIN DING ET AL.: "A unique multi-functional cationic luminescent metal–organic nanotube for highly sensitive detection of dichromate and selective high capacity adsorption of Congo red", 《RSC ADVANCES》 * |
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