CN104292249A - Covalent organic framework taking thienothiopheneboronic acid as ligand and preparation method thereof - Google Patents
Covalent organic framework taking thienothiopheneboronic acid as ligand and preparation method thereof Download PDFInfo
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- CN104292249A CN104292249A CN201410385211.1A CN201410385211A CN104292249A CN 104292249 A CN104292249 A CN 104292249A CN 201410385211 A CN201410385211 A CN 201410385211A CN 104292249 A CN104292249 A CN 104292249A
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- acid
- boric acid
- thienothiopheneboronic
- thienothiophene
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- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
Abstract
The invention relates to the technical field of organic functional materials, and especially relates to a covalent organic framework taking thienothiopheneboronic acid as a ligand. The covalent organic framework has the structural formula shown in the specification. A preparation method of the covalent organic framework taking thienothiopheneboronic acid as the ligand comprises: dissolving the thienothiopheneboronic acid ligand into a solvent of thienothiopheneboronic acid, under the reaction conditions that the temperature is 110-120 DEG C and the pressure is 1-2 MPa, reacting for 48-72 h and drying, so as to obtain the covalent organic framework taking thienothiopheneboronic acid as the ligand. The provided covalent organic framework taking thienothiopheneboronic acid as the ligand is a covalent organic framework formed through self polymerization, is regular in structure and relatively uniform in aperture ratio, is insoluble in common organic solvents, still keeps the original structure at a high temperature, and has relatively high chemical stability and thermal stability.
Description
Technical field
The present invention relates to organic functional material technical field, especially relate to a kind of covalency organic frame formed for part autohemagglutination with thienothiophene boric acid and preparation method thereof.
Background technology
The synthetic technology of framework is more and more subject to the attention of domestic and international scientist in recent years, the framework of the current overwhelming majority is metal organic frame (MOF), metal covalency organic frame (MOF) material has very large handiness in synthesis, and compound with regular structure, it is the important crystalline form porous material of a class, at gas storage and transportation, photoelectric field has a wide range of applications, but metal covalency organic frame (MOF) this kind of material also exists obvious defect, reason is because metal covalency organic frame (MOF) material is the material formed by coordinate bond by metal ion and organic ligand, its skeleton easily caves in, therefore greatly limit the widespread use of this kind of material.Since Yaghi group in 2005 reports the first covalency organic frame (COF) material, covalency organic frame (COF) causes the vast concern of various countries scientist especially, covalency organic frame (COF) has become the class type material occurred after metal-organic framework (MOFs), and development trend is instantly improvement and the regulation and control of more accurately structure prediction, NW-TFT and function.The synthesis and structure of covalency organic frame (COF) is all be formed by connecting by strong covalent bond (B-O, C-O, B-C), has the constructional feature of porous material.These materials are all by C, H, O, N, the light element compositions such as B, have specific surface area large, the advantages such as density is low, particularly have a large amount of conjugated systems, and parallel packed structures has open duct between layers, easily be excited being subject to illumination electronics, electronics easily transmits in the material, and they have potential application prospect in gas storage, catalysis, separation, optics and chemical sensitisation etc.
The covalency organic frame (COF) of the mainly copolymerization formation of current report, its synthetic reaction condition is harsher, and aperture, the duct of formation are uneven, limit the possibility that it is applied widely.Up to the present, there is not yet the report that a kind of covalency organic frame (COF) formed with thienothiophene boric acid autohemagglutination is applied in photoelectric material.
Summary of the invention
The object of the present invention is to provide a kind of with thienothiophene boric acid covalency organic frame that is part and preparation method thereof, it is a kind of covalency organic frame formed by autohemagglutination, by its temperature of reaction of strict control and reaction pressure, obtain the covalency organic frame that a kind of aperture ratio is more homogeneous, regular.
The technical solution adopted for the present invention to solve the technical problems is: a kind of covalency organic frame that is part with thienothiophene boric acid, has following structural unit:
A preparation method for the covalency organic frame being part with thienothiophene boric acid, comprises the steps:
Thienothiophene boronic acid ligands is dissolved in the solvent of thienothiophene boric acid, temperature be 110-120 DEG C, under pressure is the reaction conditions of 1-2MPa, reaction 48-72h, dries, the covalency organic frame that to obtain with thienothiophene boric acid be part.
Particularly, described solvent is Isosorbide-5-Nitrae dioxane and 1, the complex solvent of 3,5 Three methyl Benzenes.
Particularly, described Isosorbide-5-Nitrae dioxane and 1,3, the volume ratio of 5 Three methyl Benzenes is 1:0.5-3.
Particularly, described thienothiophene boric acid is thieno-[3,2-b] thiophene 2,5-boric acid or thieno-2,2-thiophene-5,5-thienyl boric acid.
The invention has the beneficial effects as follows: a kind of covalency organic frame that is part with thienothiophene boric acid provided by the invention, it is a kind of covalency organic frame formed by autohemagglutination, by its temperature of reaction of strict control and reaction pressure, obtain a kind of aperture ratio more homogeneous, regular covalency organic frame, be insoluble to and common are machine solvent, at high temperature still can keep original structure, there is higher chemical stability and thermostability, not only there is a large amount of conjugated systems, and parallel packed structures has open duct between layers, easily be excited being subject to illumination electronics, electronics easily transmits in the material, potential application prospect is had in optics and chemical sensitisation etc., it will be a kind of extraordinary photoelectric material.Provided by the invention a kind of with the preparation method of the thienothiophene boric acid covalency organic frame that is part, method is simple, easily controls, is conducive to industrialized production.
Accompanying drawing explanation
Fig. 1 is polycrystalline X-ray diffraction (PXRD) figure of covalency organic frame of the present invention, wherein A is the PXRD figure of embodiment 1 final product, B is the PXRD figure of embodiment 2 final product, C is that the PXRD of embodiment 3 final product schemes, and D is the PXRD of embodiment 4 final product.As can be seen from the figure all there is meso-hole structure at the covalency organic frame of differential responses condition gained.
Fig. 2 is the TEM figure of embodiments of the invention 1 final product.
Embodiment
Below in conjunction with specific embodiment, further the present invention is set forth, should be understood that and quote embodiment only for illustration of the present invention, and be not used in and limit the scope of the invention.
Embodiment 1
By 227mmg (1mmol) thieno-[3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml 1,4 dioxane and 1,3, in the mixing solutions of 5 Three methyl Benzene volume ratio 1:0.5, then to place it in temperature be 110 DEG C and pressure is react 48h in the autoclave of 1MPa, the product obtained filters, the solid product tetrahydrofuran (THF) filtered or acetone are carried out cleaning removing impurity, and then filter, finally its solid product is placed on 50 DEG C of vacuum drying ovens and dries, obtain 160mmg powder, productive rate 70%.As depicted in figs. 1 and 2, can find out all there is meso-hole structure at the covalency organic frame of gained.Its reaction formula is as follows:
Embodiment 2
By 227mmg (1mmol) thieno-[3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml 1,4 dioxane and 1,3, in the mixing solutions of 5 Three methyl Benzene volume ratio 1:1, then to place it in temperature be 110 DEG C and pressure is react 48h in the autoclave of 1MPa, the product obtained filters, the solid product tetrahydrofuran (THF) filtered or acetone are carried out cleaning removing impurity, and then filter, finally its solid product is placed on 50 DEG C of vacuum drying ovens and dries, obtain 168mmg powdered product, its productive rate is 74%.As shown in Figure 1, can find out all there is meso-hole structure at the covalency organic frame of gained.
Embodiment 3
By 227mmg (1mmol) thieno-[3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml 1,4 dioxane and 1,3, in the mixing solutions of 5 Three methyl Benzene volume ratio 1:3, then to place it in temperature be 110 DEG C and pressure is react 48h in the autoclave of 1MPa, the product obtained filters, the solid product tetrahydrofuran (THF) filtered or acetone are carried out cleaning removing impurity, and then filter, finally its solid product is placed on 50 DEG C of vacuum drying ovens and dries, obtain 157.7mmg powdered product, its productive rate is 69%.As shown in Figure 1, can find out all there is meso-hole structure at the covalency organic frame of gained.
Embodiment 4
By 227mmg (1mmol) thieno-[3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml 1,4 dioxane and 1,3, in the mixing solutions of 5 Three methyl Benzene volume ratio 1:1, then to place it in temperature be 120 DEG C and pressure is react 48h in the autoclave of 2MPa, the product obtained filters, the solid product tetrahydrofuran (THF) filtered or acetone are carried out cleaning removing impurity, and then filter, finally its solid product is placed on 50 DEG C of vacuum drying ovens and dries, obtain 165mmg powdered product, its productive rate is 73%.As shown in Figure 1, can find out all there is meso-hole structure at the covalency organic frame of gained.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (5)
1., with the covalency organic frame that thienothiophene boric acid is part, it is characterized in that there is following structural unit:
2., as claimed in claim 1 with a preparation method for the thienothiophene boric acid covalency organic frame that is part, it is characterized in that comprising the steps:
Thienothiophene boronic acid ligands is dissolved in the solvent of thienothiophene boric acid, temperature be 110-120 DEG C, under pressure is the reaction conditions of 1-2MPa, reaction 48-72h, dries, the covalency organic frame that to obtain with thienothiophene boric acid be part.
3. a kind of with the preparation method of the thienothiophene boric acid covalency organic frame that is part as claimed in claim 2, it is characterized in that: described solvent is Isosorbide-5-Nitrae dioxane and 1, the complex solvent of 3,5 Three methyl Benzenes.
4. a kind of with the preparation method of the thienothiophene boric acid covalency organic frame that is part as claimed in claim 3, it is characterized in that: described Isosorbide-5-Nitrae dioxane and 1,3, the volume ratio of 5 Three methyl Benzenes is 1:0.5-3.
5. a kind of with the preparation method of the thienothiophene boric acid covalency organic frame that is part as claimed in claim 2, it is characterized in that: described thienothiophene boric acid is thieno-[3,2-b] thiophene 2,5-boric acid or thieno-2,2-thiophene-5,5-thienyl boric acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440058A (en) * | 2015-11-04 | 2016-03-30 | 兰州大学 | Synthesis method for benzothiazole unit-based covalent organic framework material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102933588A (en) * | 2010-04-07 | 2013-02-13 | 康奈尔大学 | Covalent organic frameworks and methods of making same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102933588A (en) * | 2010-04-07 | 2013-02-13 | 康奈尔大学 | Covalent organic frameworks and methods of making same |
Non-Patent Citations (2)
| Title |
|---|
| DOGRU M ET AL: ""A Photoconductive Thienothiophene-Based Covalent Organic Framework Showing Charge Transfer Towards Included Fullerene"", 《ANGEW. CHEM》 * |
| SMITH M K ET AL: ""Vibrational Properties of Boroxine Anhydride and Boronate Ester Materials: Model Systems for the Diagnostic Characterization of Covalent Organic Frameworks"", 《CHEMISTRY OF MATERIALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440058A (en) * | 2015-11-04 | 2016-03-30 | 兰州大学 | Synthesis method for benzothiazole unit-based covalent organic framework material |
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Effective date of registration: 20211222 Address after: Room 407-2-6, building C, Tian'an Digital City, 588 Changwu South Road, Wujin high tech Industrial Development Zone, Changzhou City, Jiangsu Province 213100 Patentee after: CHANGZHOU XIAOGUO INFORMATION SERVICES Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |