CN105669727B - The dichloro-4,4 of azo-based benzene 2,2 ', cadmium (II) complex preparation method and the application of 4 ' dicarboxylic acids - Google Patents
The dichloro-4,4 of azo-based benzene 2,2 ', cadmium (II) complex preparation method and the application of 4 ' dicarboxylic acids Download PDFInfo
- Publication number
- CN105669727B CN105669727B CN201610023467.7A CN201610023467A CN105669727B CN 105669727 B CN105669727 B CN 105669727B CN 201610023467 A CN201610023467 A CN 201610023467A CN 105669727 B CN105669727 B CN 105669727B
- Authority
- CN
- China
- Prior art keywords
- complex
- cadmium
- solution
- dicarboxylic acids
- azo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title abstract description 57
- 150000001991 dicarboxylic acids Chemical class 0.000 title abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims abstract description 6
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract 9
- 239000013078 crystal Substances 0.000 claims description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 229940113088 dimethylacetamide Drugs 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 5
- 239000000523 sample Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002178 crystalline material Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000005595 deprotonation Effects 0.000 claims 1
- 238000010537 deprotonation reaction Methods 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 238000001917 fluorescence detection Methods 0.000 abstract description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- -1 moon Ion Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- KPWJBEFBFLRCLH-UHFFFAOYSA-L Cadmium bromide Inorganic materials Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 1
- OKIIEJOIXGHUKX-UHFFFAOYSA-L Cadmium iodide Inorganic materials [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention relates to a kind of dichloro-4,4 of azo-based benzene 2,2 ', cadmium (II) complex of 4 ' dicarboxylic acids and preparation method thereof.The coordination chemistry formula is [Cd (L) (DMA)] (H2O)0.5, synthetic method is：Under normal temperature and pressure, it is first at room temperature that cadmium nitrate (II) metal salt is soluble in water, stir, form solution (I), thereafter, part HL is dissolved in N, in N ' dimethylacetylamides (abbreviation DMA), stir, form solution (II), solution (I), (II) are poured into the stainless steel cauldron with polytetrafluoroethylliner liner, the complex that the present invention is reported is obtained after heated sealed a couple of days.The complex has the advantages that good thermal stability, and operation is simple for synthetic method, product yield is high, it is repeatable high the advantages of.The material is to contained Co in solution2+Ion embodies significant fluorescence quenching capability, is expected in Co2+Ion fluorescence detection field is further developed.
Description
Technical field
The present invention relates to d10Metal complex fluorescent Material Field, is a kind of azobenzene -2,2 '-two chloro- 4,4 '-dicarboxyl
Acid-cadmium (II) complex and preparation method thereof, the complex has (the 4 of single node 6- connections12.63) topology network architecture,
Co in methanol solvate can be applied to as fluorescence probe2+The detection of ion.
Background technology
Azobenzene -4,4 '-dicarboxylic acids refer to benzoic acid by nitrogen nitrogen double bond (- N=N-) connect and formed carry carboxyl official
The multidentate ligand that can be rolled into a ball, in an assembling process, azobenzene provide rigid support to construct coordination framework, and carboxyl can be cooperation
The construction of thing provides diversified coordination mode, because azobenzene structure has conjugated pi system, in ultraviolet light to visible infrared
Wave band has very strong absorption, shows colourful color, therefore is widely used for preparing all kinds of complexs, for synthesizing
Dyestuff, toner etc..With azobenzene -4,4 '-dicarboxylic acids is compared, azobenzene -2,2 '-two chloro- 4, the related ligand of 4 '-dicarboxylic acids
Polymer research is then less.The especially chloro- 4,4 '-dicarboxylic acids of '-two of azobenzene -2,2 and d10What transition metal ions was formed matches somebody with somebody
Compound is also unmanned so far to be reported.In addition, at present by azobenzene -2,2 '-two chloro- 4,4 '-dicarboxylic acids complex is applied to detection Co2+
The fluorescence probe field of ion does not have trial also.In view of this, inventor spy proposes a kind of azobenzene -2, and 2 '-two is chloro-
Cd (II) complex preparation technologies of 4,4 '-dicarboxylic acids and its for Co2+The fluorescence detection method of ion, to fill up domestic foreign minister
The blank in pass field.
The content of the invention
It is an object of the invention to propose a kind of chloro- 4,4 '-dicarboxylic acids of '-two of azo-based benzene-2,2-cadmium (II) complex
And preparation method thereof, the complex can be as fluorescent material application, and heat endurance is good, and its preparation method is simple and easy to do, yield
Height, reproducibility is good, so as to overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme：
A kind of azo-based benzene -2,2 '-two chloro- 4,4 '-dicarboxylic acids-cadmium (II) complex, it is characterised in that the cooperation
Thing has following chemical formula, i.e.,：[Cd(L)(DMA)](H2O)0.5, wherein L is azobenzene -2,2 '-two chloro- 4,4 '-dicarboxylic acids the moon
Ion ligand, L skeleton symbol is as follows：
Further speaking, the complex crystal belongs to tetragonal crystal system, and space group isI41/a, cell parameter isa =
24.5828(5) Å, b = 24.5828(5) Å, c = 14.1353(5) Å, α = 90 o, β = 90 o, γ = 90o, V = 8542.2(5) Å3。
The complex crystal has three-dimensional net structure, wherein, each central atom Cd (II) is former with part carboxyl oxygen
Son forms metal cluster and is connected by part with six metal cluster centers.
A kind of azo-based benzene -2 as described above, 2 '-two chloro- 4, the preparation method of cadmium (II) complex of 4 '-dicarboxylic acids,
This method is：
It is at room temperature that metal salt cadmium nitrate (II) is soluble in water first, stir, form solution (I), thereafter, will
Part HL is dissolved in N, N '-dimethyl acetamide, is stirred, and forms solution (II), solution (I), (II) are poured into volume
In 20 milliliters of stainless steel cauldrons with polytetrafluoroethylliner liner, to form hydro-thermal reaction system after sealing.The hydro-thermal reaction body
HL parts and the mol ratio of cadmium (II) salt are 1 in system:1~1: 2.5；
Hydro-thermal reaction system is placed in baking oven and is heated to 95~120oC, keeping temperature is constant, is slowly dropped to after three days
Room temperature, obtains orange rhabdolith.Suction filtration, washing, drying process are carried out to it successively, target product is obtained.Specifically：
Cd in the metal cadmium salt solution soluble in water being made2+Concentration be 0.01~0.08 mol L-1。
The part HL is dissolved in N, in the solution of N '-dimethyl acetamide formation the concentration of contained HL parts for 0.01~
0.04 mol∙L-1。
The volume ratio of N in the dicyandiamide solution of the N, N '-dimethyl acetamide and water, N '-dimethyl acetamide and water is
1:0.9~1: 2.1.The temperature of reaction system is 95~120oC。
This method is comprised the following specific steps that：
（1）It is at room temperature that metal salt cadmium nitrate (II) is soluble in water first, stir, form solution (I), thereafter,
Part HL is dissolved in N, N '-dimethyl acetamide, stirred, solution (II) is formed, solution (I), (II) is poured into body
Accumulate in 20 milliliters of stainless steel cauldrons with polytetrafluoroethylliner liner, to form hydro-thermal reaction system after sealing, the hydro-thermal reaction
Contained HL and the mol ratio of cadmium (II) metal salt are 1 in system:1~1:2.5, and wherein Cd2+Concentration be 0.01~0.08
mol∙L-1；The volume ratio of N, N '-dimethyl acetamide and water is 1:0.9~1:2.1, wherein, N, N '-dimethyl acetamide contains
0.01~0.04 mol L-1Part HL；Hydro-thermal reaction system is placed in baking oven and is heated to 95~120oC, keeping temperature is not
Become, slow near room temperature, obtains orange rhabdolith after three days.Suction filtration, washing, drying process are carried out to it successively, mesh is obtained
Mark product.
The cadmium (II) that the present invention synthesizes a kind of chloro- 4,4 '-dicarboxylic acids of '-two of azo-based benzene -2,2 using hydro-thermal method coordinates
Thing, its course of reaction is basic to be carried out under high temperature, high pressure, and fidelity factor is high, and gained thermal analysis is good, yield is high, is expected to
It is used widely in fluorescent crystal Material Field.Described fluorescent crystal material is referred to for Co2+The fluorescent crystal of detection
Material.
Brief description of the drawings：
Fig. 1 is in embodiment 1~5 in cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2
Cd (II) coordination context diagram；
Fig. 2 is cadmium (II) the complex edge of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2 in embodiment 1~5
CrystallographycThe three-dimensional net structure figure in direction；
Fig. 3 is cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2 in embodiment 1~5
Single node 6- connections (412.63) topological schematic diagram；
Fig. 4 is that cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2 in embodiment 1~5 is matched somebody with somebody
The solid state fluorescence spectrogram of compound；
Fig. 5 is cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2 in embodiment 1~5
The experiment of X-ray powder diffraction (PXRD) and theoretical compares figure；
Fig. 6 is cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2 in embodiment 1~5
Thermal gravimetric analysis curve figure.
Fig. 7 is cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2 in embodiment 1~5
To Co in methanol solvate2+The fluorescent quenching figure of ion.
Embodiment
In the preparation method of complex of the present invention, part HL（Reagent Company is on sale）It is dissolved in N, N '-dimethyl acetamide
In solution is made, its concentration be 0.01~0.04 mol L-1；Cadmium (II) metal salt is soluble in water to be made solution, and its concentration is
0.02~0.08 mol L-1；The volume ratio of N, N '-dimethyl acetamide and water is 1:0.9~1: 2.1.
Embodiment 1
The preparation technology of cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of the azo-based benzene -2,2 '-two is as follows：
Weigh 0.10 mmol Cd (NO3)2·4H2O is placed in beaker, is distilled water dissolves with 3.0 mL, is stirred, shape
Into solution (I)；0.05 mmol HL are weighed in beaker with 3.0 mL N, N '-dimethyl acetyl amine solvent stirs, shape
Into solution (II)；Solution (I), (II) are poured into volume in 20 milliliters of stainless steel cauldrons with polytetrafluoroethylliner liner, it is close
It is honored as a queen and ultimately forms hydro-thermal reaction system, hydro-thermal reaction system is placed in baking oven and is heated to 100oC, keeping temperature is constant, and three
Slow near room temperature after it, polytetrafluoroethylene (PTFE) tank bottom obtains orange bar-like single crystal, and the crystal is used into distilled water and N, N '-two successively
Methylacetamide is washed, vacuum drying, that is, obtains target product, its yield is about 62%.
The main infrared absorption peak of the target product is：1633s, 1596s, 1489w, 1406vs, 1258w,
1196m, 1127w, 1034m, 961w, 904m, 842w, 818m, 788m, 747w, 690w, 638m, 616m,
588w, 539w, 479w, 430m；Its elementary analysis result is：Theoretical value: C, 39.62; H, 2.96;N, 9.78%,
Experiment value: C, 39.57; H, 2.98;N, 9.81%.
Embodiment 2
The preparation technology of cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of the azo-based benzene -2,2 '-two is as follows：
Weigh 0.12 mmol Cd (NO3)2·4H2O is placed in beaker, is distilled water dissolves with 3.5 mL, is stirred, shape
Into solution (I)；0.10 mmol HL are weighed in beaker with 4.0 mL N, N '-dimethyl acetyl amine solvent stirs, shape
Into solution (II)；Solution (I), (II) are poured into volume in 20 milliliters of stainless steel cauldrons with polytetrafluoroethylliner liner, it is close
It is honored as a queen and ultimately forms hydro-thermal reaction system, hydro-thermal reaction system is placed in baking oven and is heated to 95oC, keeping temperature is constant, and three
Slow near room temperature after it, polytetrafluoroethylene (PTFE) tank bottom obtains orange bar-like single crystal, and the crystal is used into distilled water and N, N '-two successively
Methylacetamide is washed, vacuum drying, that is, obtains target product, its yield is about 60%.
The main infrared absorption peak of the target product is：1632s, 1597s, 1487w, 1405vs, 1257w,
1197m, 1126w, 1033m, 962w, 903m, 843w, 819m, 787m, 747w, 692w, 637m, 616m,
587w, 536w, 477w, 431m；Its elementary analysis result is：Theoretical value: C, 39.62; H, 2.96;N, 9.78%,
Experiment value: C, 39.60; H, 2.93;N, 9.72%.
Embodiment 3
The preparation technology of cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of the azo-based benzene -2,2 '-two is as follows：
Weigh 0.20 mmol Cd (NO3)2·4H2O is placed in beaker, is distilled water dissolves with 4.5 mL, is stirred, shape
Into solution (I)；0.20 mmol HL are weighed in beaker with 5.0 mL N, N '-dimethyl acetyl amine solvent stirs, shape
Into solution (II)；Solution (I), (II) are poured into volume in 20 milliliters of stainless steel cauldrons with polytetrafluoroethylliner liner, it is close
It is honored as a queen and ultimately forms hydro-thermal reaction system, hydro-thermal reaction system is placed in baking oven and is heated to 120oC, keeping temperature is constant, and three
Slow near room temperature after it, polytetrafluoroethylene (PTFE) tank bottom obtains orange bar-like single crystal, and the crystal is used into distilled water and N, N '-two successively
Methylacetamide is washed, vacuum drying, that is, obtains target product, its yield is about 61.5%.
The main infrared absorption peak of the target product is：1633s, 1596vs, 1488w, 1406s, 1258w,
1195m, 1127w, 1033m, 962w, 904m, 843w, 816m, 786m, 748w, 691w, 638m, 616m,
588m, 539w, 479w, 430m；Its elementary analysis result is：Theoretical value： C, 39.62; H, 2.96;N, 9.78%, it is real
Test value: C, 39.55; H, 2.99;N, 9.75%.
Embodiment 4
The preparation technology of cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of the azo-based benzene -2,2 '-two is as follows：
Weigh 0.10 mmol CdBr2It is placed in beaker, distills water dissolves with 3.0 mL, stir, forms solution
(I)；0.05 mmol HL are weighed in beaker with 3.0 mL N, N '-dimethyl acetyl amine solvent stirs, form solution
(II)；Solution (I), (II) are poured into volume in 20 milliliters of stainless steel cauldrons with polytetrafluoroethylliner liner, after sealing most
Hydro-thermal reaction system is placed in baking oven into hydro-thermal reaction system and is heated to 115 by end formoC, keeping temperature is constant, delays after three days
Slow near room temperature, polytetrafluoroethylene (PTFE) tank bottom obtains orange bar-like single crystal, and the crystal is used into distilled water and N, N '-dimethyl second successively
Acid amides is washed, vacuum drying, that is, obtains target product, its yield is about 65%.
The main infrared absorption peak of the target product is：1630s, 1596vs, 1489m, 1405vs, 1257w,
1195m, 1127m, 1034m, 961w, 904m, 842w, 816m, 788m, 746w, 690w, 638m, 616m,
588w, 539w, 479m, 430m；Its elementary analysis result is：Theoretical value： C, 39.62; H, 2.96;N, 9.78%, it is real
Test value： C, 39.59; H, 2.93; N, 9.81%.
Embodiment 5
The preparation technology of cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of the azo-based benzene -2,2 '-two is as follows：
Weigh 0.15 mmol CdI2It is placed in beaker, distills water dissolves with 3.0 mL, stir, forms solution (I)；
0.15 mmol HL are weighed in beaker with 6.0 mL N, N '-dimethyl acetyl amine solvent stirs, form solution (II)；
Solution (I), (II) are poured into volume in 20 milliliters of stainless steel cauldrons with polytetrafluoroethylliner liner, to ultimately form after sealing
Hydro-thermal reaction system, hydro-thermal reaction system is placed in baking oven and is heated to 110oC, keeping temperature is constant, slow near after three days
Room temperature, polytetrafluoroethylene (PTFE) tank bottom obtains orange bar-like single crystalI41/a, the crystal is used into distilled water and N, N '-dimethyl second successively
Acid amides is washed, vacuum drying, that is, obtains target product, its yield is about 58%.
The main infrared absorption peak of the target product is：1631s, 1595vs, 1487m, 1406vs, 1258w,
1196m, 1127w, 1033m, 962w, 904m, 843w, 818w, 788m, 747m, 690m, 638m, 616m,
588w, 539w, 479w, 430m；Its elementary analysis result is：Theoretical value： C, 39.62; H, 2.96;N, 9.78%, it is real
Test value: C, 39.69; H, 2.93; N, 9.72%.
Embodiment 6
The fluorescence respective behavior of complex：
30 mg complex is ground, is placed in after compression molding in solid state fluorescence photometer, using the nm of excitation wavelength 320
Tested, obtain the nm of launch wavelength 395 maximum emission peak.
Embodiment 7
Complex is to Co2+Fluorescent quenching behavior：It is parallel by 1 mg complex ultrasonic disperse in 5 ml methanol solution
It is two parts, and 1 mmol Co of a addition thereto2+In solution, it is placed in fluophotometer, using the nm of excitation wavelength 410
Tested, add Co2+The sample of solution occurs in that fluorescent quenching phenomenon.
The cadmium (II) of the chloro- 4,4 '-dicarboxylic acids of '-two of gained azo-based benzene -2,2 is matched somebody with somebody in following Example 1~4 respectively
Compound is further characterized, and its process is as follows：
（1）The crystal structure determination of complex
The monocrystalline for choosing suitable size under the microscope carries out X-ray diffraction experiment at room temperature.In Bruker Apex
On II CCD diffractometers, with the Mo-K through graphite monochromator monochromatizationαRay (λ=0.71073), is collected in φ-ω modes
Diffraction data is collected into 10484 point diffractions altogether.Crystal structure is solved by direct method using SHELXS-97 programs, non-hydrogen atom
Obtained by difference Fourier synthetic method.Whole non-hydrogen atom coordinates and anisotropic parameters carry out complete matrix least square method and repaiied
Just, hydrogen atom position is pressed theoretical mode computation and determined.Detailed axonometry data are shown in Table 1, important bond distance and bond angle data
It is shown in Table 2.Crystal structure is shown in Fig. 1 and Fig. 2, and the topological schematic diagram of complex is shown in Fig. 3.
（2）The solid fluorescence performance study of complex
Complex crystal sample after enrichment processing, by further milled processed, carries out the test of solid fluorescence：Coordinate
Thing is excited at 320 nm, and the emission peak of maximum is obtained at 395 nm, Fig. 4 (INSTRUMENT MODELs are seen：Varian, Cary
Eclipse)。
（3）The X-ray powder diffraction (PXRD) of complex is characterized
The PXRD of complex, which is characterized, shows that it has reliable phase purity, and guarantor is provided as the application of fluorescent material for it
Card, is shown in Fig. 5 (INSTRUMENT MODELs：Rigaku, D/Max-2500).
（4）The thermal stability of complex is characterized
The thermogravimetric analysis of complex, which is characterized, shows it close to 246oC or so remains to stable existence, with higher heat surely
It is qualitative, provide heat endurance as the further development and application of crystalline material for it and ensure, see Fig. 6 (INSTRUMENT MODELs：
Siemens, NETZSCH TG209).
It can see by above-mentioned characterization result, complex crystal of the present invention belongs to tetragonal crystal system, space group isI41/a, cell parameter isa = 24.5828(5) Å, b = 24.5828(5) Å, c = 14.1353(5) Å, α = 90o, β
= 90 o, γ = 90 o, V = 8542.2(5) Å3.Basic structure is a novel three-dimensional net structure, in asymmetric list
In member, comprising two Cd atoms, wherein Cd (II) only has a kind of coordination environment, is hexa-coordinate octoploids structure, each Cd (II)
Atom respectively with four ligand moleculars, the coordination of two solvent molecules, can in order to clearly illustrate the three-dimensional net structure of complex
To be abstracted into topological structure：Each central atom Cd (II) passes through part and six with part carboxyl oxygen atom formation metal cluster
Individual metal cluster is connected, so 6- connecting nodes can be simplified to.Thus, the three-dimensional net structure of the complex can be simplified as
(the 4 of one single node 6- connection12.63) topological network.
The predominant crystal data of the complex of table 1
Main bond distance's () of the complex of table 2 and bond angle [°] *
Above example is merely to illustrate present disclosure, in addition, and the present invention also has other embodiment.But
It is that the technical scheme that all use equivalent or equivalent deformation mode are formed is all fallen within protection scope of the present invention.
Claims (3)
1. a kind of azo-based benzene-two chloro- 4, cadmium (II) complex of 4 '-dicarboxylic acids, it is characterised in that the complex has
Following chemical formula, i.e.,：[Cd(L)(DMA)](H2O)0.5, wherein DMA is N, and N '-dimethyl acetamide, L is carboxyl deprotonation
Azobenzene-two chloro- 4,4 '-dicarboxylic acids anion ligand, L skeleton symbol is as follows：
And the complex crystal belongs to tetragonal crystal system, space group isI41/a, cell parameter isa = 24.5828(5) Å, b
= 24.5828(5) Å, c = 14.1353(5) Å, α= 90o, β= 90 o, γ= 90 o, V = 8542.2(5) Å3。
2. azo-based benzene-two chloro- 4 described in claim 1, the preparation method of cadmium (II) complex of 4 '-dicarboxylic acids, this method
For：
It is at room temperature that cadmium nitrate (II) is soluble in water first, stir, solution (I) is formed, thereafter by part H2L is dissolved in
In N, N '-dimethyl acetamide, stir, form solution (II), it is poly- for 20 milliliters of bands that solution (I), (II) are poured into volume
In the stainless steel cauldron of tetrafluoroethene inner bag, hydro-thermal reaction system is formed after sealing；Part H in the hydro-thermal reaction system2L with
The mol ratio of cadmium nitrate (II) is 1:1~1: 2.5；Hydro-thermal reaction system is placed in baking oven and is heated to 95~120oC, is protected
Hold temperature-resistant, room temperature is slowly dropped to after three days, obtain orange rhabdolith；It is carried out successively suction filtration, washing, dry at
Reason, obtains target product；
Cd in the wherein described cadmium nitrate solution soluble in water being made2+Concentration be 0.01~0.08 mol L-1；The part
H2L is dissolved in contained H in N, the solution of N '-dimethyl acetamide formation2The concentration of L parts is 0.01~0.04 mol L-1；It is described
The volume ratio of N in the dicyandiamide solution of N, N '-dimethyl acetamide and water, N '-dimethyl acetamide and water is 1:0.9~1:
2.1。
3. cadmium (II) complex of the chloro- 4,4 '-dicarboxylic acids of azo-based benzene-two described in claim 1 is preparing Co2+Fluorescence probe
Application in terms of crystalline material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610023467.7A CN105669727B (en) | 2016-01-15 | 2016-01-15 | The dichloro-4,4 of azo-based benzene 2,2 ', cadmium (II) complex preparation method and the application of 4 ' dicarboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610023467.7A CN105669727B (en) | 2016-01-15 | 2016-01-15 | The dichloro-4,4 of azo-based benzene 2,2 ', cadmium (II) complex preparation method and the application of 4 ' dicarboxylic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105669727A CN105669727A (en) | 2016-06-15 |
| CN105669727B true CN105669727B (en) | 2017-07-18 |
Family
ID=56300673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610023467.7A Expired - Fee Related CN105669727B (en) | 2016-01-15 | 2016-01-15 | The dichloro-4,4 of azo-based benzene 2,2 ', cadmium (II) complex preparation method and the application of 4 ' dicarboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105669727B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294560B (en) * | 2018-11-06 | 2021-04-27 | 洛阳师范学院 | Supramolecular azobenzene-2, 2' -aluminum diformate metal gel luminescent material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789211A (en) * | 2015-03-30 | 2015-07-22 | 吉林化工学院 | Preparation method for azobenzene-4,4'-dicarboxylic acid cadmium complex with blue light performance |
-
2016
- 2016-01-15 CN CN201610023467.7A patent/CN105669727B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789211A (en) * | 2015-03-30 | 2015-07-22 | 吉林化工学院 | Preparation method for azobenzene-4,4'-dicarboxylic acid cadmium complex with blue light performance |
Non-Patent Citations (3)
| Title |
|---|
| 3, 3′-偶氮-二(6-羟基苯甲酸)镉和钴的配合物: [Cd(OSA)(Phen)(H2O)]n和[Co(OSA)(Phen)(H2O)]n 的合成、表征及晶体结构;唐云志等;《无机化学学报》;20071231;第23卷(第1期);第70-74页 * |
| A multifunctional microporous anionic metal–organic framework for column-chromatographic dye separation and selective detection and adsorption of Cr3+;Shu-Ran Zhang et al;《Journal of Materials Chemistry A》;20151012;第3卷;第23426-23434页 * |
| Tuning the structures of three coordination polymers incorporating ZnII and 2,2’-dichloro-4,4’-azodibenzoic acid via selective auxiliary;Xiao-Ping Zeng et al;《Journal of Molecular Structure》;20150702;第1099卷;第 441-445页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105669727A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107474060B (en) | It is a kind of with the metal-organic framework materials and its preparation method and application for being selectively adsorbing and separating anionic dye performance | |
| CN107417926A (en) | Template is oriented to Porous coordination polymer and its preparation and application of synthesis | |
| CN110343259A (en) | A kind of interlayer type zinc coordination polymer of green fluorescence and the preparation method and application thereof | |
| CN105646552A (en) | Zn(II) complex based on 5-hydroxynictinic acid and preparation method and application thereof | |
| CN106188108B (en) | The metal-organic framework materials and preparation method and applications of a kind of Cd | |
| CN102942580A (en) | Zinc 5-methyl isophthalate complex and preparation method thereof | |
| Li et al. | A lanthanide metal–organic framework as ratio fluorescence probe to detect pesticides in water | |
| CN106349282A (en) | 3,3',4,5'-biphenyl tetracarboxylic acid and 4,4'-bipyridine mixed cadmium-lead complex and preparation method and application thereof | |
| CN107312026B (en) | With the rare earth samarium complex and preparation method of photocatalytic degradation of dye function and application | |
| CN105669727B (en) | The dichloro-4,4 of azo-based benzene 2,2 ', cadmium (II) complex preparation method and the application of 4 ' dicarboxylic acids | |
| CN103113415B (en) | Thermostability Ni title complex with fluorescence property and preparation method thereof | |
| CN107739442A (en) | The synthesis and application for the metal organic framework compound constructed based on the dicarboxylic acids of pyridine 2,5 and 4,4 ' bipyridyls | |
| CN113265065B (en) | Cadmium-based metal-organic framework with fluorescence recognition function on Al3+ and Ga3+ ions and preparation method thereof | |
| CN109232667A (en) | A kind of magnetism dinuclear cobalt complex and its preparation method and application | |
| CN108424429B (en) | Cd (II) and K (I) complex with three-dimensional porous structure and preparation method and application thereof | |
| CN108929442A (en) | Based on the sour ligand para-terpheny -3,4 of rigidity three ", the metallo-organic compound and its preparation method and application of 5- tricarboxylic acids | |
| CN104341440B (en) | 4-tert-butyl o phthalic acid Zn complex and preparation method thereof | |
| CN105461747A (en) | Novel micropore-organic skeleton metal lead complex as well as preparation method and application thereof | |
| CN109651620A (en) | A kind of nickel metal coordinating polymer and preparation method thereof | |
| Naskar et al. | Synthesis, crystal structure and spectroscopic properties of an oximato bridged cu (II) dimer | |
| CN105503938B (en) | Pb (II) complexs and its synthetic method based on 5 bromo-nicotinic acids | |
| CN107286201A (en) | Stable chain Ni (II) complexes of amino acid with fluorescence property and preparation method thereof | |
| CN104610327A (en) | Gadolinium complex with high stability and high magnetocaloric effect as well as preparation method of gadolinium complex | |
| CN108424527A (en) | The synthetic method of Zn (II) complex of three-dimensional hybrid ligand and fluorescence probe application | |
| CN104292246A (en) | 4-methyl zinc phthalate complex and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170718 Termination date: 20190115 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |