CN110862404A - Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof - Google Patents
Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof Download PDFInfo
- Publication number
- CN110862404A CN110862404A CN201911143876.0A CN201911143876A CN110862404A CN 110862404 A CN110862404 A CN 110862404A CN 201911143876 A CN201911143876 A CN 201911143876A CN 110862404 A CN110862404 A CN 110862404A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- metal
- bipyridyl
- acid
- crystal material
- 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.)
- Pending
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 70
- 239000013078 crystal Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 64
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- WLWKIJKUDWYINL-UHFFFAOYSA-N cyclohexane-1,1,2,2,3,3-hexacarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O WLWKIJKUDWYINL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 10
- DTGRIEIJTWNZQF-UHFFFAOYSA-N cyclohexane-1,2,3,4,5,6-hexacarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C(C(O)=O)C(C(O)=O)C1C(O)=O DTGRIEIJTWNZQF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 238000012377 drug delivery Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- -1 4' -bipyridyl Chemical compound 0.000 claims abstract description 6
- 230000005611 electricity Effects 0.000 claims abstract description 5
- 230000005389 magnetism Effects 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims description 45
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 20
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 20
- 239000002178 crystalline material Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000000144 pharmacologic effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 description 1
- FSVJFNAIGNNGKK-UHFFFAOYSA-N 2-[cyclohexyl(oxo)methyl]-3,6,7,11b-tetrahydro-1H-pyrazino[2,1-a]isoquinolin-4-one Chemical compound C1C(C2=CC=CC=C2CC2)N2C(=O)CN1C(=O)C1CCCCC1 FSVJFNAIGNNGKK-UHFFFAOYSA-N 0.000 description 1
- 241000242678 Schistosoma Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940121657 clinical drug Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229960002957 praziquantel Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
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 System
- C07F3/06—Zinc compounds
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of metal-organic framework crystal materials, and particularly relates to a metal-organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and a preparation method thereof. Putting 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid, 4' -bipyridyl, zinc nitrate, water, ethanol, methanol or acetone into a high-pressure reaction kettle with a polytetrafluoroethylene lining, adjusting the pH value to 9 by using NaOH, ultrasonically mixing uniformly, reacting for three days while keeping the temperature at 120 ℃, and naturally cooling to room temperature. Filtering and washing to obtain colorless blocky crystals. The invention creates a novel three-dimensional metal-organic framework crystal material with a reticular structure, which has the advantages of excellent luminescence property, simple synthesis method, convenient operation, high yield, good reproducibility and the like. And has application value in various fields such as gas storage, trapping, separation, drug delivery, light, electricity, magnetism, selective catalysis, molecular recognition, chiral resolution and the like.
Description
Technical Field
The invention belongs to the technical field of metal-organic framework crystal materials, and particularly relates to a metal-organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl, and a preparation method thereof.
Background
The metal-organic skeleton crystal material belongs to one kind of supermolecular compound and is the product of the combination of crystal engineering theory and supermolecular chemistry. It has two advantages of inorganic and organic, and the change of organic ligand can make the molecular sieve structure implement diversified structure and adjustable pore channel, so that it can implement directional design. Research on novel molecular functional materials spans a plurality of fields of crystal engineering, material chemistry, topology, inorganic chemistry, organic chemistry, supramolecular chemistry, coordination chemistry, physicochemical, and the like. The material has a crystalline structure with zeolite-like molecular sieve-like pore channel rules, also has a higher specific surface area than that of the traditional porous material, and additionally contains organic components, so that the structure of the material has the characteristics of cuttability, designability, pore channel size adjustment, functional pore channel surface and the like, and the material has excellent performances in various fields of host-guest chemistry, gas storage, trapping, separation, drug delivery, optical, electrical and magnetic departments, selective catalysis, molecular recognition, chiral resolution and the like. In recent years, metal-organic framework crystalline materials have become one of the hot spots for the research of new functionalized materials. Recently, some metal-organic framework crystalline materials have been successfully commercialized.
1,2,3,4,5, 6-cyclohexane hexacarboxylic acid is an important intermediate for synthesizing various medicaments, is an important organic synthetic raw material, is mainly used for synthesizing medicines, pesticides, dyes and other organic compounds, and is used for synthesizing a new drug for resisting pregnancy 392 and treating schistosome, namely praziquantel; it can also be used as vulcanized rubber compatibilizer, petroleum clarifier, etc.
4, 4' -bipyridine is a common intermediate for medicine and organic synthesis, and can be used for determining iron content and liquid crystal materials. The zinc metal has good photoelectric and electromagnetic properties and the ability of promoting the growth and development of human body and enhancing immunity.
In view of the above, the present inventors have specifically proposed a cyclohexane-hexacarboxylic acid and bipyridine-based metal-organic framework crystal material and a preparation method thereof, which not only retains chemical and pharmacological properties of each ligand, but also forms a network structure, and has stable fluorescence properties, and thus has application values in various fields such as gas storage, trapping, separation, drug delivery, optical, electrical, magnetic, selective catalysis, molecular recognition, chiral resolution, and the like.
Disclosure of Invention
In order to overcome the problems in the background art, the invention provides a metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and a preparation method thereof, wherein the material not only retains the chemical and pharmacological properties of each ligand, but also forms a three-dimensional metal-organic framework crystal material structure with a net structure, and has application values in various fields of gas storage, trapping, separation, drug delivery, light, electricity, magnetism, selective catalysis, molecular recognition, chiral resolution and the like. .
In order to realize the purpose, the invention is realized by the following technical scheme:
the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl: 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid is used as a ligand A, 4' -bipyridine is used as a ligand B and is coordinated with metal zinc to form a basic structural unit of the metal-organic framework crystal material; the basic structure unit structure of the metal-organic framework crystal material comprises a divalent zinc ion, two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acids are used as ligands and two 4, 4' -bipyridyl ligands; wherein, zinc ions are in a hexacoordination form, four oxygen atoms and two nitrogen atoms which are respectively coordinated with the zinc ions are respectively from three monodentate coordinated carboxyl oxygen atoms provided by two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligands, one water oxygen atom and two heterocyclic nitrogen atoms provided by two 4, 4' -bipyridyl ligands; two 4, 4' -bipyridine ligands are perpendicular to each other and are separated from zinc along the ab planeTwo 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligands are mutually vertical and are coordinated with zinc ions along a bc plane; each ligand is extended outwards and coordinated with other zinc ions and ligands to form a three-dimensional metal-organic framework material crystal structure with a net structure along the C-axis direction, the chemical formula of the three-dimensional metal-organic framework material crystal structure is C22H17N2O13Zn, the three-dimensional metal-organic framework material belongs to monoclinic crystal (monoclinic), and the unit cell parameters are as follows:
α＝90°，β＝90.861(11)°，γ＝90°,
Z＝4。
further, the metal organic framework crystal material based on the cyclohexane hexacarboxylic acid and the bipyridyl is formed by combining a 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligand, a 4, 4' -bipyridyl ligand and metal zinc ions in a molar ratio of 2:2: 1.
The preparation method of the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is characterized by comprising the following steps of:
(1) adding 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligand, 4' -bipyridyl ligand, zinc nitrate and organic solvent in a molar ratio of 0.5:0.5: 1-4: 4:1 into a high-pressure reaction kettle for reaction;
(2) placing the high-pressure reaction kettle on an ultrasonic device, and ultrasonically mixing for 1-4 hours at room temperature;
(3) and after stirring is stopped, placing the high-pressure reaction kettle in an oven at the temperature of 40-120 ℃ for 10-40 hours, taking out, cooling to room temperature, and separating out massive colorless crystals, namely the metal organic framework crystal material based on the cyclohexane hexacarboxylic acid and the bipyridyl.
Further, the organic solvent is selected from one or more of methanol, ethanol, isopropanol, ethyl acetate, acetone and acetonitrile.
Further, the reaction temperature of the step (1) is 40-120 ℃.
Further, the ultrasonic blending time in the step (2) is 2 hours.
Further, the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is applied to gas storage, trapping and separation.
Further, the metal organic framework crystal material based on the cyclohexane hexacarboxylic acid and the bipyridyl is applied to drug delivery.
Further, the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is applied to the fields of light, electricity and magnetism.
Further, the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is applied to the fields of selective catalysis, molecular recognition and chiral resolution.
The invention has the beneficial effects that:
the metal-organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl prepared by the invention not only retains the chemical and pharmacological properties of each ligand, but also forms a network structure, has stable fluorescence performance, and has application value in various fields such as gas storage, trapping, separation, drug delivery, light, electricity, magnetism, selective catalysis, molecular recognition, chiral separation and the like.
Drawings
FIG. 1: the invention discloses a schematic diagram of a metal-organic framework crystal material structural unit;
FIG. 2: the invention relates to a microscope structure diagram of a metal-organic framework crystal material;
FIG. 3: a spatial three-dimensional network diagram of the metal-organic framework crystal material of the invention;
FIG. 4: the metal-organic framework crystal material is simulated to obtain an XRD spectrogram;
FIG. 5: the solid state fluorescence spectrum of the metal-organic framework crystal material is shown.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings to facilitate understanding of the skilled person.
The invention selects 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid as ligand A, 4' -bipyridyl as ligand B to coordinate with metal zinc and prepares a novel three-dimensional metal-organic framework crystal material with a net structure in solvents such as water, ethanol, methanol or acetone and the like.
1,2,3,4,5, 6-cyclohexane hexacarboxylic acid and 4, 4' -bipyridine are organic carboxylic acids which are clinical drugs and drug synthesis precursors, and the molecular formulas are respectively as follows: C12H12O 12; C10H8N2, and the structural formula is shown in formulas a and b.
The metal-organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is a basic structural unit of the metal-organic framework crystal material formed by coordination of 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid serving as a ligand A and 4, 4' -bipyridyl serving as a ligand B and metal zinc; the basic structure unit structure of the metal-organic framework crystal material comprises a divalent zinc ion, two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acids are used as ligands and two 4, 4' -bipyridyl ligands; wherein, zinc ions are in a hexacoordination form, four oxygen atoms and two nitrogen atoms which are respectively coordinated with the zinc ions are respectively from three monodentate coordinated carboxyl oxygen atoms provided by two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligands, one water oxygen atom and two heterocyclic nitrogen atoms provided by two 4, 4' -bipyridyl ligands; two 4, 4' -bipyridyl ligands are mutually vertical and coordinated with zinc ions along an ab plane, and two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligands are mutually vertical and coordinated with zinc ions along a bc plane; each ligand is extended outwards and coordinated with other zinc ions and ligands to form a three-dimensional metal-organic framework material crystal structure with a net structure along the C-axis direction, the chemical formula of the three-dimensional metal-organic framework material crystal structure is C22H17N2O13Zn, the three-dimensional metal-organic framework material belongs to monoclinic crystal (monoclinic), and the unit cell parameters are as follows:
α＝90°，β＝90.861(11)°，γ＝90°,
and Z is 4. The three-dimensional metal-organic framework crystal material of the 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid and the 4,4 '-bipyridyl is formed by combining a 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligand, a 4, 4' -bipyridyl ligand and metal zinc ions according to a molar ratio of 2:2: 1.
Example 1
Preparation of metal organic framework crystalline material based on cyclohexanehexocarboxylic acid and bipyridine:
adding 0.2mmol of 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid, 0.2mmol of 4, 4' -bipyridyl and 0.1mmol of zinc nitrate into a mixed solvent consisting of 3ml of water and 3ml of ethanol, placing the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and ultrasonically mixing the mixture for 2 hours at room temperature; after the ultrasonic treatment is stopped, the high-pressure reaction kettle is placed in an oven at the temperature of 80 ℃ and is placed for 20 hours, then the high-pressure reaction kettle is taken out, and after the high-pressure reaction kettle is cooled to room temperature, massive colorless crystals are separated out, and the molar yield is 85%.
Example 2
Preparation of metal organic framework crystalline material based on cyclohexanehexocarboxylic acid and bipyridine:
adding 0.2mmol of 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid, 0.2mmol of 4, 4' -bipyridyl and 0.1mmol of zinc nitrate into a mixed solvent consisting of 3ml of water and 3ml of methanol, placing the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and ultrasonically mixing the mixture for 2 hours at room temperature; after the ultrasonic treatment is stopped, the high-pressure reaction kettle is placed in an oven at the temperature of 80 ℃ and is placed for 20 hours, then the high-pressure reaction kettle is taken out, and after the high-pressure reaction kettle is cooled to the room temperature, massive colorless crystals are separated out, and the molar yield is 88%.
Example 3
Preparation of metal organic framework crystalline material based on cyclohexanehexocarboxylic acid and bipyridine:
adding 0.2mmol of 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid, 0.2mmol of 4, 4' -bipyridyl and 0.1mmol of zinc nitrate into a mixed solvent consisting of 3ml of water and 3ml of acetone, placing the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and ultrasonically mixing the mixture for 2 hours at room temperature; after the ultrasonic treatment is stopped, the high-pressure reaction kettle is placed in an oven at the temperature of 80 ℃ and is placed for 20 hours, then the high-pressure reaction kettle is taken out, and after the high-pressure reaction kettle is cooled to the room temperature, massive colorless crystals are separated out, and the molar yield is 80%.
Characterization of the crystal structure of a metal-organic framework crystal material based on cyclohexanehexocarboxylic acid and bipyridine:
the crystal structure was determined using a Bruker Apex II CCD diffractometer at 296(2) K using MoK α radiation monochromatized with graphite
Diffraction points were collected in an omega scan fashion, and the collected data were reduced by the SAINT program and corrected for semi-empirical absorption using the SADABS method. The structure analysis and the refinement are respectively completed by using SHELXS and SHELXL of a SHELXTL program, and F2 is corrected by a full matrix least square method to obtain the coordinates and the anisotropic parameters of all non-hydrogen atoms. All hydrogen atoms are theoretically fixed on the parent atom during the structure refinement process, giving an isotropic displacement parameter slightly (C-H, 1.2 or O/N-H, 1.5 times) larger than the parent atom displacement parameter. The detailed crystal determination data are shown in Table 1, the schematic diagram of the structural units is shown in Table 1,
the structure diagram of a microscope of the metal organic framework crystal material based on the cyclohexane hexacarboxylic acid and the bipyridyl is shown in figure 2, the space three-dimensional network diagram of the metal organic framework crystal material based on the cyclohexane hexacarboxylic acid and the bipyridyl is shown in figure 3, and the simulated powder diffraction diagram of the metal organic framework crystal material based on the cyclohexane hexacarboxylic acid and the bipyridyl is shown in figure 4.
Table 1 cocrystal principal crystallographic data
Solid fluorescence property research of metal organic framework crystal materials based on cyclohexane hexacarboxylic acid and bipyridyl:
samples of metal-organic framework crystalline materials based on cyclohexanehexocarboxylic acid and bipyridine were subjected to a test for solid fluorescence: the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is excited by light at 300nm through fluorescence spectrum analysis, and has a strong fluorescence absorption peak at 383nm light wave. Accordingly, the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl can be further applied as a fluorescent material, see figure 5.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is characterized in that: 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid is used as a ligand A, 4, 4' -bipyridyl is used as a ligand B to be coordinated with metal zinc to form a basic structural unit of the metal-organic framework crystal material; the basic structure unit structure of the metal-organic framework crystal material comprises a divalent zinc ion, two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acids are used as ligands, and two 4, 4' -bipyridyl are used as ligands; wherein, zinc ions are in a hexacoordination form, four oxygen atoms and two nitrogen atoms which are respectively coordinated with the zinc ions are respectively from three monodentate coordinated carboxyl oxygen atoms provided by two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligands, one water oxygen atom and two heterocyclic nitrogen atoms provided by two 4, 4' -bipyridyl ligands; two 4, 4' -bipyridyl ligands are mutually vertical and coordinated with zinc ions along an ab plane, and two 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligands are mutually vertical and coordinated with zinc ions along a bc plane; each ligand is extended outwards in coordination with other zinc ions and ligands to form a three-dimensional metal-organic framework material crystal structure with a net structure along the c-axis direction;
the specific crystallographic data of the metal-organic framework material crystal are as follows: c22H17N2O13Zn, monoclinic, a=10.2907(12)Å，b= 11.3531(10) Å，c= 20.047(3) Å，α= 90°，β= 90.861(11)°，γ= 90°, V= 2341.8(4) Å3, Z =4。
2. The cyclohexanehexocarboxylic acid and bipyridine-based metal-organic framework crystalline material according to claim 1, characterized in that: the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is formed by combining 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligand, 4' -bipyridyl ligand and metal zinc ions according to the molar ratio of 2:2: 1.
3. The cyclohexanehexocarboxylic acid and bipyridine-based metal-organic framework crystalline material according to claim 1, characterized in that: the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is applied to gas storage, trapping and separation.
4. The cyclohexanehexocarboxylic acid and bipyridine-based metal-organic framework crystalline material according to claim 1, characterized in that: the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is applied to drug delivery.
5. The cyclohexanehexocarboxylic acid and bipyridine-based metal-organic framework crystalline material according to claim 1, characterized in that: the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is applied to the fields of light, electricity and magnetism.
6. The cyclohexanehexocarboxylic acid and bipyridine-based metal-organic framework crystalline material according to claim 1, characterized in that: the metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl is applied to the fields of selective catalysis, molecular recognition and chiral resolution.
7. The method for preparing metal organic framework crystalline material based on cyclohexane-hexacarboxylic acid and bipyridine as claimed in claim, comprising the following steps:
1) adding 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid ligand, 4' -bipyridyl ligand and zinc nitrate in a molar ratio of 0.5:0.5: 1-4: 4:1, and water and ethanol, methanol or acetone in a volume ratio of 4: 1-1: 4 into a high-pressure reaction kettle with a polytetrafluoroethylene lining;
2) placing the high-pressure reaction kettle on an ultrasonic device, and ultrasonically mixing for 2 hours at room temperature;
3) and after stirring is stopped, placing the high-pressure reaction kettle in an oven at the temperature of 40-120 ℃ for 10-40 hours, taking out, cooling to room temperature, and separating out massive colorless crystals, namely the three-dimensional metal-organic framework crystal material based on 1,2,3,4,5, 6-cyclohexane hexacarboxylic acid and 4, 4' -bipyridyl.
8. The method for preparing a metal-organic framework crystalline material based on cyclohexanehexocarboxylic acid and bipyridine according to claim 7, wherein: the organic solvent is selected from methanol, ethanol, isopropanol, ethyl acetate, acetone, and acetonitrile.
9. The method for preparing a metal-organic framework crystalline material based on cyclohexanehexocarboxylic acid and bipyridine according to claim 7, wherein: the stirring time is 1-4 h.
10. The method for preparing a metal-organic framework crystalline material based on cyclohexanehexocarboxylic acid and bipyridine according to claim 7, wherein: the reaction temperature is 40-120 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910261392 | 2019-04-02 | ||
| CN201910261392X | 2019-04-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110862404A true CN110862404A (en) | 2020-03-06 |
Family
ID=69655252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911143876.0A Pending CN110862404A (en) | 2019-04-02 | 2019-11-20 | Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110862404A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603897A (en) * | 2021-08-25 | 2021-11-05 | 北京工业大学 | Preparation of zinc-based metal organic framework material and selective adsorption application thereof |
| CN114561022A (en) * | 2022-03-08 | 2022-05-31 | 兰州大学 | Chiral Cd-MOFs material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299475A (en) * | 2018-02-06 | 2018-07-20 | 云南农业大学 | 3-dimensional metal based on 5- chlorothiophene -2- carboxylic acids and 4,4 '-bipyridyls-organic backbone crystalline material and preparation method |
-
2019
- 2019-11-20 CN CN201911143876.0A patent/CN110862404A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299475A (en) * | 2018-02-06 | 2018-07-20 | 云南农业大学 | 3-dimensional metal based on 5- chlorothiophene -2- carboxylic acids and 4,4 '-bipyridyls-organic backbone crystalline material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| RONGMING WANG等: "A Zn Metal−Organic Framework with High Stability and Sorption Selectivity for CO2" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603897A (en) * | 2021-08-25 | 2021-11-05 | 北京工业大学 | Preparation of zinc-based metal organic framework material and selective adsorption application thereof |
| CN113603897B (en) * | 2021-08-25 | 2022-06-07 | 北京工业大学 | Preparation of zinc-based metal organic framework material and selective adsorption application thereof |
| CN114561022A (en) * | 2022-03-08 | 2022-05-31 | 兰州大学 | Chiral Cd-MOFs material and preparation method thereof |
| CN114561022B (en) * | 2022-03-08 | 2023-01-03 | 兰州大学 | Chiral Cd-MOFs material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105985362B (en) | A kind of method for preparing zeolite imidazole ester frame structure material | |
| CN107698625B (en) | Synthesis and application of metal organic framework compound constructed based on thiophene-2, 5-dicarboxylic acid and phenanthroline | |
| WO2013033922A1 (en) | Metal nickel-imidazole chiral nano clathrate complex and preparation process thereof | |
| CN104230968B (en) | Cadmium-containing dual-core polymer with mixed-ligand and preparation method of cadmium-containing dual-core polymer | |
| CN108997383B (en) | Metal organic framework compound and preparation method and application thereof | |
| CN108947813B (en) | Process for preparing two-dimensional MOF material by one-step solvothermal method | |
| CN110862404A (en) | Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof | |
| CN109824911B (en) | Indium-potassium-copper trimetal coordination polymer crystal and preparation method and application thereof | |
| CN110590858B (en) | Cobalt-containing coordination compound with low-temperature phase change and preparation method thereof | |
| CN105884805B (en) | A kind of Cd (II) mixture coordination polymer and preparation method thereof | |
| CN112592486B (en) | Cd (II) coordination polymer with two-dimensional supramolecular structure and preparation method thereof | |
| CN102827195B (en) | Rare-earth organic coordination polymer constructed by using m-phthalic acid and 2-pyridylformic acid as mixed ligand, and preparation method and application thereof | |
| CN110862549A (en) | Three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine and preparation method thereof | |
| CN104292247B (en) | A kind of have mixed ligand containing cadmium two-dimensional polymer and preparation method thereof | |
| CN106083851B (en) | A kind of metallic lead complex with low temperature phase change, preparation method and applications | |
| CN109369691B (en) | High-temperature phase change compound and preparation method and application thereof | |
| CN108341970B (en) | Coordination polymer based on 2, 5-thiophenedicarboxylic acid and gadolinium and preparation method thereof | |
| CN102827194A (en) | Rare-earth organic coordination polymer using 2,2'-dipyridine as auxiliary ligand and template, and preparation method and application thereof | |
| Rekik et al. | New transition metal sulfates templated by 1, 4-butanediamine,(C4H14N2)[MII (H2O) 6](SO4) 2· 4H2O (MII: Co, Ni): Structure, reactivity and thermal decomposition | |
| CN104193784A (en) | Coordination compound with ferroelectric properties, as well as preparation method and application thereof | |
| CN111116929B (en) | Nickel coordination polymer material with wide-temperature-zone reversible thermochromic property and preparation method and application thereof | |
| CN113980286A (en) | Synthesis method and application of Ni-based coordination polymer | |
| CN109092361B (en) | Rare earth metal organic complex based on chalcone dicarboxylic acid ligand and preparation method and application thereof | |
| CN106995467A (en) | A kind of method that microwave catalysis synthesizes bicycloplatin | |
| CN108341969B (en) | Coordination polymer based on 2, 5-thiophenedicarboxylic acid and lanthanum and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200306 |
|
| RJ01 | Rejection of invention patent application after publication |