CN103242370A - Metal organic gel based on tetrazole compounds - Google Patents
Metal organic gel based on tetrazole compounds Download PDFInfo
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- CN103242370A CN103242370A CN2013101637065A CN201310163706A CN103242370A CN 103242370 A CN103242370 A CN 103242370A CN 2013101637065 A CN2013101637065 A CN 2013101637065A CN 201310163706 A CN201310163706 A CN 201310163706A CN 103242370 A CN103242370 A CN 103242370A
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Abstract
The invention belongs to the field of supramolecular chemistry, and in particular relates to a coordination polymer gel (metal organic gel) formed based on tetrazole compounds and palladium acetate, and a preparation method of the metal organic gel. The framework of the tetrazole compounds comprise the structures of aryl, alkyl, porphyrin ring and the like; the tetrazole groups contain single tetrazole to four tetrazole; the tetrazole compounds and palladium acetate form irreversible metal organic gel in a solvent N,N-dimethylformamide or N,N-dimethylacetamide; and the tetrazole compounds do not have the characteristic of forming gel in the used solvent system. The used methyl tetrazole compound is the compound with minimal molecular weight, and the gel formed by the tetrazole compound and the palladium acetate is the simplest known coordination polymer gel at present.
Description
Technical field
The invention belongs to the supramolecular chemistry field.Be specifically related to a class based on tetrazole compound and palladium form ligand polymer gel (being the metal organogel) and preparation method thereof.
Background technology
Metal organogel, i.e. ligand polymer gel.Different with simple organogel is, this gellike at first must generate ligand polymer by the coordination between organic ligand and the metal ion, and then the parcel solvent forms gel, this just makes it possess the not available unique physical chemical property of a lot of organogels, therefore cause the great interest of people about the development of metal organogel in recent years, and obtained a lot of outstanding achievements.Traditionally, organic ligand unit in the most metal organogel all needs some specific auxiliary groups to promote the generation of gelation, such as chain alkyl, ether chain, aryl etc., the major cause that increases these groups is that they can provide gelation process needed non covalent bond reactive force, as hydrogen bond, pi-pi accumulation, Fan Dehuali etc.But the synthetic organic ligand unit that is introduced as of these auxiliary groups has brought a lot of inconvenience, has also limited the development in metal organogel field simultaneously.So this exist is an extremely important and challenging job at present: the organic ligand unit is tending towards oversimplifying.That is to say that we need invent the simple organic ligand that does not need auxiliary group, utilize itself and metal ion to interact and form the ligand polymer gel.
In recent years, the development of the coordination chemistry of tetrazole compound was comparatively rapid, had also obtained good application aspect a lot.Tetrazole compound belongs to Five-membered Heterocyclic Compounds, owing to contain a plurality of nitrogen-atoms and have aromaticity, tetrazyl and pyridine, cyano group is the same potential purposes when synthetic ligand polymer, the nitrogen-atoms that a plurality of haptos can be provided is arranged on the ring, they both can be used as neutral molecule and had participated in coordination, can under the effect of alkali, lose proton plays balancing charge as negatively charged ion effect again, simultaneously, nitrogen-atoms also can be used as proton donor (Donor) or acceptor (Acceptor) and forms hydrogen bond action and construct super molecular compound based on hydrogen bond.The research about the supramolecular chemistry of tetrazole compound at present mainly concentrates on (W-T Liu, J-Y Li, Z-P Ni, Y-C Ou, J-D Leng, J-L Liu, Crystal Growth﹠amp on the crystalline material; Design, 2012,12,1482; M-G Liu, P-P Zhang, J Peng, H-X Meng, X Wang, M Zhu, Crystal Growth﹠amp; Design, 2012,12,1273.), and this compounds is few in the application in gel field.Therefore, the development for supramolecular chemistry has great significance based on the metal organogel of tetrazole compound in research.
Summary of the invention
The object of the present invention is to provide ligand polymer gel that a class forms based on tetrazole compound and palladium and preparation method thereof.
The structure of tetrazole compound and the preparation method of metal organogel are described respectively below:
Tetrazole compound is characterised in that a plurality of nitrogen-atoms that hapto is provided on the tetrazole ring, can form metal coordinating polymer with metal ion, and its general structure is:
In the formula: R can be methyl, chain alkyl, branched-chain alkyl, phenyl ring, pyridine ring, is with substituent phenyl ring or pyridine ring, nitrogen benzide, porphyrin and metal complexes thereof etc.
The typical method of the gelation process test of described metal organogel is: the reversing test tube method.Its concrete operations are: tetrazole compound and palladium are mixed by a certain percentage be dissolved in respectively in the solvent (N, dinethylformamide or N,N-dimethylacetamide), mix then and leave standstill for some time.If test tube is inverted, the mouth of pipe is downward, and sample did not flow and was equal phase this moment, then thinks gel formation.
In order to achieve the above object, the present invention by the following technical solutions: tetrazolium functional group is that 1:1 to 2:1 reaction all can form gel with the ratio of palladium.
The concrete steps of tetrazolium class ligand polymer preparing gel of the present invention are: tetrazole compound and palladium are dissolved in N respectively, dinethylformamide or N, in the N-N,N-DIMETHYLACETAMIDE, mix then, leave standstill and to obtain pale brown look transparent irreversible gel a moment.
Characteristics of the present invention are: tetrazole compound itself does not have into the characteristic of gel, but because it has a plurality of nitrogen-atoms that hapto can be provided, can form stable irreversible metal organogel with palladium.No matter be the methyl tetrazolium of molecular weight minimum, the tetrazolium part of rigidity, the tetrazolium part of band azo functional group, the tetrazolium part of band long alkyl chain, the tetrazolium part of band porphyrin ring and the porphyrin tetrazolium part that there is metal at the center, they and palladium are done the time spent and can both be generated the yellow transparent gel.Result of study shows that these colloids can steady in a long-termly exist, stablize and reach the several months, thereby constituted the simple ligand polymer gel of the structure factor, wherein the methyl tetrazolium is the compound of molecular weight minimum, and the gel that itself and palladium form is present the simplest known ligand polymer gel.
One-tenth glue mechanism according to organogel, the contrast experiment who does in conjunction with us, it is the fact that the tetrazole compound described in the present invention can not form gel with Palladous chloride, can infer that acetate ion has also played certain promoter action for the formation of gel except coordination has taken place for tetrazol group and palladium ion.
Show according to atomic force microscope and transmission electron microscope results, tetrazolium and palladium form title complex to be assembled in dilute solution and has formed a series of spherical particles, when concentration increased, spherical particle was further assembled and has been formed reticulated structure, thereby organic solvent is wrapped up the formation gel.
Description of drawings
Fig. 1 is the atomic force microscope images (height map and phasor) of gel 1
Fig. 2 is the images of transmissive electron microscope of gel 2
Embodiment
Following case study on implementation is used for explanation the present invention.Should be pointed out that these embodiment only are used for illustrating the present invention rather than restriction the present invention.
Embodiment 1
In tool plug test tube, add 30mg compound 1(methyl tetrazolium, R=CH
3), adding 1mL N, dinethylformamide dissolves solid fully; Add the 82.1mg palladium in another brace plug test tube, add 1mL N, dinethylformamide dissolves solid fully, then with the two mixing, leaves standstill and can generate pale brown look clear gel 1 a moment.
From then on the AFM height map of gel and phasor (as shown in Figure 1) we can see a lot of tightly packed small-particles together, mean diameter is about 45nm, the particle formation network structure that closely connects together, thereby solvent is wrapped up the formation gel.
Embodiment 2
In tool plug test tube, add 30mg compound 2(n-octyl tetrazolium, R=C
8H
17), adding 1mL N, dinethylformamide dissolves solid fully; Add the 28.3mg palladium in another brace plug test tube, add 1mL N, dinethylformamide dissolves solid fully, then with the two mixing, leaves standstill and can generate pale brown look clear gel 2 a moment.
The transmission electron microscope situation of this gel, as shown in Figure 2, on the copper mesh of same sample, we have observed three kinds of patterns, and a kind of is relative dispersed particles, and a kind of is intensive relatively particle, at last a kind of then is the particle that links together, and almost is extended to a kind of reticulated structure.We infer that this is thereby that this netted structure can play effective parcel organic solvent formation stable gel.
Embodiment 3
Adding 50mg compound 3(contains the porphyrin ring of four tetrazoliums in tool plug test tube, and its molecular formula is as follows), add 1mL N, dinethylformamide dissolves solid fully; Add the 12.5mg palladium in another brace plug test tube, add 1mL N, dinethylformamide dissolves solid fully, then with the two mixing, leaves standstill and can generate pale brown look clear gel 3 a moment.
。
Claims (5)
1. the tetrazolium class ligand polymer gel factor is characterised in that it contains a plurality of nitrogen-atoms and has aromaticity, and a plurality of nitrogen-atoms that hapto can be provided are arranged on the tetrazole ring, can form the metal organogel with metal, and its general structure is:
In the formula: R can be methyl, chain alkyl, branched-chain alkyl, phenyl ring, pyridine ring, is with substituent phenyl ring or pyridine ring, nitrogen benzide, porphyrin and metal complexes thereof etc.
2. the technical scheme of ligand polymer preparing gel according to claim 1 is: tetrazolium functional group is that 1:1 to 2:1 reaction all can form gel with the ratio of palladium.
3. the concrete steps of ligand polymer preparing gel according to claim 1 are: tetrazole compound and palladium are dissolved in N respectively, dinethylformamide or N, in the N-N,N-DIMETHYLACETAMIDE, mix then, leave standstill and to obtain pale brown look clear gel a moment.
4. ligand polymer gel according to claim 1, it is characterized in that: tetrazole compound itself does not have into the characteristic of gel, but because it has a plurality of nitrogen-atoms that hapto can be provided, can form stable irreversible metal organogel with palladium.
5. ligand polymer gel according to claim 1, it is characterized in that: no matter be the methyl tetrazolium of molecular weight minimum, the tetrazolium part of rigidity, the tetrazolium part of band azo functional group, the tetrazolium part of band long alkyl chain, the tetrazolium part of band porphyrin ring and the porphyrin tetrazolium part that there is metal at the center, they and palladium are done the time spent and can both be generated the yellow transparent gel.Result of study shows that these colloids can steady in a long-termly exist, and stablizes to reach the several months.Thereby constituted the simple ligand polymer gel of the structure factor, wherein the methyl tetrazolium is the compound of molecular weight minimum, and the gel that itself and palladium form is present the simplest known ligand polymer gel.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399750A (en) * | 2015-12-11 | 2016-03-16 | 西北师范大学 | Tetrazole porphyrin metal complexes, synthesis thereof and applications of the metal complexes as dye sensitizing agents |
| CN109135060A (en) * | 2018-08-17 | 2019-01-04 | 丹阳博亚新材料技术服务有限公司 | A kind of foamed heat-insulating material and preparation method thereof based on polypropylene matrix |
| CN115505133A (en) * | 2022-09-20 | 2022-12-23 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Hydrogen bond organic framework and preparation method and application thereof |
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| US20040019031A1 (en) * | 1993-10-15 | 2004-01-29 | Duke University | Oxidant scavengers |
| CN102532189A (en) * | 2012-01-12 | 2012-07-04 | 西北师范大学 | Preparation method of super-molecule metal gel |
| WO2013001235A1 (en) * | 2011-06-30 | 2013-01-03 | Centre National De La Recherche Scientifique | Supported alkoxylated organotin reactant, preparation and use for heterogeneous-phase synthesis of tetrazoles |
| CN102924397A (en) * | 2012-09-27 | 2013-02-13 | 西南石油大学 | Dual-component micromolecular organic gel |
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2013
- 2013-05-07 CN CN2013101637065A patent/CN103242370A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| US20040019031A1 (en) * | 1993-10-15 | 2004-01-29 | Duke University | Oxidant scavengers |
| WO2013001235A1 (en) * | 2011-06-30 | 2013-01-03 | Centre National De La Recherche Scientifique | Supported alkoxylated organotin reactant, preparation and use for heterogeneous-phase synthesis of tetrazoles |
| CN102532189A (en) * | 2012-01-12 | 2012-07-04 | 西北师范大学 | Preparation method of super-molecule metal gel |
| CN102924397A (en) * | 2012-09-27 | 2013-02-13 | 西南石油大学 | Dual-component micromolecular organic gel |
Non-Patent Citations (1)
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| POLIVINA JOLICIA F. GAUUAN: "Superoxide Dismutase Mimetics: Synthesis and Structure–Activity Relationship Study of MnTBAP Analogues", 《BIOORGANIC & MEDICINAL CHEMISTRY》, vol. 10, no. 9, 28 May 2002 (2002-05-28) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399750A (en) * | 2015-12-11 | 2016-03-16 | 西北师范大学 | Tetrazole porphyrin metal complexes, synthesis thereof and applications of the metal complexes as dye sensitizing agents |
| CN105399750B (en) * | 2015-12-11 | 2018-07-17 | 西北师范大学 | Tetrazole porphyrin metal complex and its synthesis and application as dye sensitizing agent |
| CN109135060A (en) * | 2018-08-17 | 2019-01-04 | 丹阳博亚新材料技术服务有限公司 | A kind of foamed heat-insulating material and preparation method thereof based on polypropylene matrix |
| CN109135060B (en) * | 2018-08-17 | 2023-03-28 | 丹阳博亚新材料技术服务有限公司 | Foamed heat-insulating material mainly based on polypropylene matrix and preparation method thereof |
| CN115505133A (en) * | 2022-09-20 | 2022-12-23 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Hydrogen bond organic framework and preparation method and application thereof |
| CN115505133B (en) * | 2022-09-20 | 2023-10-24 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Hydrogen bond organic framework and preparation method and application thereof |
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Application publication date: 20130814 |