CN105541886A - Carborane-containing metal-organic framework and preparation method thereof - Google Patents
Carborane-containing metal-organic framework and preparation method thereof Download PDFInfo
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- CN105541886A CN105541886A CN201510563725.6A CN201510563725A CN105541886A CN 105541886 A CN105541886 A CN 105541886A CN 201510563725 A CN201510563725 A CN 201510563725A CN 105541886 A CN105541886 A CN 105541886A
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Abstract
The invention discloses a carborane-containing metal-organic framework and a preparation method thereof. The metal-organic framework is prepared through coordinating modified carborane and metal ions. The preparation method comprises the following steps: 1, preparing the modified carborane; and 2, adding the modified carborane to a solvent to prepare a modified carborane solution, mixing the modified carborane solution with a metal salt solution in proportion under magnetic stirring, and reacting under heating and sealing for 1-5h. The carborane-containing metal-organic framework has the advantages of good high temperature resistance and high long-term use temperature.
Description
Technical field
The present invention relates to Metal-organic frame field, particularly relate to a kind of containing carborane Metal-organic frame and preparation method thereof.
Background technology
Metal-organic framework material (MetalOrganicFrameworks, MOFs) makes again metal organic coordination polymer (MetalOrganicCoordinationPolymers, MOCPs) become a kind of novel functionalized crystal material.It inorganic metal center (metal ion or metal ion bunch) is coupled together the crystalline material of the network-like structure forming unlimited extension by organic bridgingligand with crossing the mode of coordinate bond.Inorganic chemistry and organic chemistry two kinds are considered as two kinds of diverse chemistry subjects and combine dexterously by metal-organic framework material usually.Extend situation according to metal-organic framework material at Spatial Dimension and metal-organic framework material is divided into one-dimensional chain, two-dimensional layer, three-dimensional space network shape structure.
The maximum feature of metal-organic framework material is exactly it is porosity (free volume up to 90%) and the huge inner ratio surface area (exceeding 6000 meters squared per gram) that a kind of crystalline material has superelevation.And making its various structures and adjustable due to the structure of inorganic and organic heterogeneity composition, these finally impel metal-organic framework material to have potential application in many aspects.Its high porosity is such as utilized to store various different energy gas (hydrogen, methane, second block) or catch carbon dioxide cleaning air, the utilization of this direct relation clean energy and the protection of environment.By utilizing its adjustable hole size, shape is separated various valuable gases as being separated from nitrogen by carbonic acid gas with hole surface functional group, second block is separated from methane, acetylene is separated with carbonic acid gas with rare being separated of second, methane, and carbonic acid gas is separated with nitrogen, various different carbonatoms (C1, C2, C3) the separation of hydrocarbon gas molecule, inert gas krypton is separated with Yin.This structural performance be made up of inorganic metal ion or metal ion bunch and organic bridgingligand due to metal-organic framework material makes it have the feature of inorganic materials and organic materials, make it in chemical sensor, second-order nonlinear optical material, luminescent material, all has good application in ferroelectric material.In addition, metal-organic framework material also can have application at heterogeneous asymmetry catalysis and Drug absorbability and slowly-releasing.Why metal-organic framework material can have application in so numerous, to be combined by inorganic chemistry and have excellent controllability just because of it with organic chemistry.By regulate change organic bridgingligand or inorganic tie point just can the structures and characteristics of correspondingly regulable control metal-organic framework material.Metal-organic framework material as a kind of Multifunction material also pay close attention to by increasing chemist.
But the resistance to elevated temperatures of existing metal-organic framework material and life-time service temperature need to improve.
Summary of the invention
The technical problem that the present invention mainly solves is to provide one containing carborane Metal-organic frame and preparation method thereof, can improve the high thermal resistance of Metal-organic frame, improves life-time service temperature.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: provide that a kind of it is prepared by carbon modified borine and metallic ion coordination containing carborane Metal-organic frame, described carbon modified borine structure as shown in the formula (I),
（I）
Wherein R is C
1-4alkyl, A is the one in sulfonic group, amino and carboxyl.
In a preferred embodiment of the present invention, described metal ion is transition metal ion.
In a preferred embodiment of the present invention, described transition metal ion is iron, silver or cupric ion.
In a preferred embodiment of the present invention, described carbon modified borine is boron modified by 1,12-bis-carbon-to-carbon.
For solving the problems of the technologies described above, another technical solution used in the present invention is: provide a kind of preparation method containing carborane Metal-organic frame, comprise the following steps:
(1) preparation of carbon modified borine as shown in the formula (II), R
1for alkyl, aryl, M is Li, Na, K or MgX, and X is F, Cl, Br or I; R is C
1-4alkyl, A is the one in sulfonic group, amino and carboxyl;
（II）
(2) carbon modified borine is added in solvent make carbon modified Borane solution, under magnetic stirring, carbon modified Borane solution is proportionally mixed with metal salt solution, under heated sealant, react 1-5h.
In a preferred embodiment of the present invention, described solvent is DMF or water-ethanol, and wherein water and ethanol contend are than being 1:(1-2).
In a preferred embodiment of the present invention, described carbon modified Borane solution mixes according to the ratio that volume ratio is 1:1 with metal salt solution.
In a preferred embodiment of the present invention, the volumetric molar concentration of described carbon modified Borane solution is 5-25mmol/L.
In a preferred embodiment of the present invention, the volumetric molar concentration of described metal salt solution is 1-5mmol/L.
In a preferred embodiment of the present invention, the Heating temperature in step (2) is 60-80 DEG C.
Carborane in the present invention is the cage structure being formed icosahedron electron deficiency " super aromaticity " by two carbon atoms and ten boron atoms, whole cage molecule is stablized, cage structure volume is huge simultaneously, to adjacent group, there is shielding effect, so have high thermostability, water-fast, chemical-resistant stability is also fabulous, be fitted together in polymeric amide and also can obtain good performance, as improved its thermostability, processing characteristics etc.
The invention has the beneficial effects as follows: the present invention has good high thermal resistance, higher life-time service temperature.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings, wherein:
Fig. 1 is the fluorometric investigation result of Metal-organic frame prepared by amino modified carborane and europium ion.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
Under nitrogen atmosphere, by 5.11g(0.035mol) 1,12-bis-carbon-to-carbon borine adds in 20mL benzene, continue to add 4.5g(0.071mol) n-Butyl Lithium ice bath under react 2h after, add 12g(0.072mol) 4-bromo-butyric acid reaction 4h after, filtration obtains carboxy-modified carborane 5.91g(0.027mol), productive rate is 77%;
By 2.18g(0.010mol) obtained carboxy-modified carborane adds the N of 675mL, the carboxy-modified carborane solution that volumetric molar concentration is 15mmol/L is obtained in dinethylformamide solvent, under magnetic stirring, be the carboxy-modified carborane solution of 15mmol/L by 100mL volumetric molar concentration, be that 5mmol/L iron nitrate solution mixes with 100mL volumetric molar concentration, reaction vessel is airtight, filter after 70 DEG C of isothermal reaction 4h, obtain Metal-organic frame prepared by carboxy-modified carborane and iron ion.
Embodiment 2
Under nitrogen atmosphere, by 5.11g(0.035mol) 1,12-bis-carbon-to-carbon borine adds in 20mL benzene, continue to add 4.5g(0.071mol) n-Butyl Lithium ice bath under react 2h after, add 11.41g(0.072mol) 3-chlorine propanesulfonic acid reaction 4h after, filtration obtains sulfonic group modified carborane 7.74g(0.029mol), productive rate is 83%;
By 2.67g(0.010mol) obtained sulfonic group modified carborane adds in the water-ethanol solvent of 1250mL volume ratio 1:1 that to obtain volumetric molar concentration be the sulfonic group modified carborane solution of 8mmol/L, under magnetic stirring, be the sulfonic group modified carborane solution of 8mmol/L by 100mL volumetric molar concentration, be that 4mmol/L copper nitrate solution mixes with 100mL volumetric molar concentration, reaction vessel is airtight, filter after 65 DEG C of isothermal reaction 5h, obtain Metal-organic frame prepared by sulfonic group modified carborane and cupric ion.
Embodiment 3
Under nitrogen atmosphere, by 5.11g(0.035mol) 1,12-bis-carbon-to-carbon borine adds in 20mL benzene, continue to add 4.5g(0.071mol) n-Butyl Lithium ice bath under react 2h after, add 6.73g(0.072mol) 3-chlorine propylamine reaction 4h after, filtration obtains amino modified carborane 7.02g(0.027mol), productive rate is 77%;
By 2.60g(0.010mol) to add 835mL volume ratio be that to obtain volumetric molar concentration in the water-ethanol solvent of 1:1.5 be 12mmol/L amino modified carborane solution to obtained amino modified carborane, under magnetic stirring, be the sulfonic group modified carborane solution of 12mmol/L by 100mL volumetric molar concentration, be that 4mmol/L europium chloride solution mixes with 100mL volumetric molar concentration, reaction vessel is airtight, filter after 65 DEG C of isothermal reaction 5h, obtain Metal-organic frame prepared by amino modified carborane and europium ion.Because Europium Metal has fluorescence property, the fluorometric investigation result of this Metal-organic frame as shown in Figure 1.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical field, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1., containing a carborane Metal-organic frame, it is characterized in that, it is prepared by carbon modified borine and metallic ion coordination, described carbon modified borine structure as shown in the formula (I),
（I）
Wherein R is C
1-4alkyl, A is the one in sulfonic group, amino and carboxyl.
2. according to claim 1 containing carborane Metal-organic frame, it is characterized in that, described metal ion is transition metal ion.
3. according to claim 1 containing carborane Metal-organic frame, it is characterized in that, described transition metal ion is iron, silver or cupric ion.
4. according to claim 1 containing carborane Metal-organic frame, it is characterized in that, described carbon modified borine is boron modified by 1,12-bis-carbon-to-carbon.
5. the preparation method containing carborane Metal-organic frame according to claim 1, is characterized in that, comprise the following steps:
(1) preparation of carbon modified borine as shown in the formula (II), R
1for alkyl, aryl, M is Li, Na, K or MgX, and X is F, Cl, Br or I; R is C
1-4alkyl, A is the one in sulfonic group, amino and carboxyl;
（II）
(2) carbon modified borine is added in solvent make carbon modified Borane solution, under magnetic stirring, carbon modified Borane solution is proportionally mixed with metal salt solution, under heated sealant, react 1-5h.
6. according to claim 5 containing carborane Metal-organic frame, it is characterized in that, described solvent is DMF or water-ethanol, and wherein water and ethanol contend are than being 1:(1-2).
7. according to claim 5 containing carborane Metal-organic frame, it is characterized in that, described carbon modified Borane solution mixes according to the ratio that volume ratio is 1:1 with metal salt solution.
8. according to claim 5 containing carborane Metal-organic frame, it is characterized in that, the volumetric molar concentration of described carbon modified Borane solution is 5-25mmol/L.
9. according to claim 5 containing carborane Metal-organic frame, it is characterized in that, the volumetric molar concentration of described metal salt solution is 1-5mmol/L.
10. according to claim 5 containing carborane Metal-organic frame, it is characterized in that, the Heating temperature in step (2) is 60-80 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008584A (en) * | 2016-06-01 | 2016-10-12 | 哈尔滨工业大学无锡新材料研究院 | Method for controlling carborane derivative structure by click reaction |
| CN109851810A (en) * | 2019-03-22 | 2019-06-07 | 浙江大学 | A kind of borane anion supermolecule organic framework materials and its preparation method and application |
| CN111471190A (en) * | 2020-05-21 | 2020-07-31 | 南京工业大学 | Covalent organic framework material with carborane as starting material and preparation method and application thereof |
Citations (1)
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|---|---|---|---|---|
| US20090025556A1 (en) * | 2007-07-27 | 2009-01-29 | Northwestern University | Metal-Organic Framework Materials Based on Icosahedral Boranes and Carboranes |
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Patent Citations (1)
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| US20090025556A1 (en) * | 2007-07-27 | 2009-01-29 | Northwestern University | Metal-Organic Framework Materials Based on Icosahedral Boranes and Carboranes |
Non-Patent Citations (4)
| Title |
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| FARHA O K. ET AL: ""Synthesis and Hydrogen Sorption Properties of Carborane Based Metal-Organic Framework Materials"", 《J. AM. CHEM. SOC》 * |
| HEYING B T L. ET AL: ""A New Series of Organoboranes.111. Some Reactions of 1,2-Dicarbaclovododecaborane(l2) and its Derivatives"", 《INORGANIC CHEMISTRY》 * |
| LEE J D. ET AL: ""Practical Synthesis of Aminoethyl-o-carboranes"", 《ORGANOMETALLICS》 * |
| SUSAN L W. ET AL: ""Multinuclear platinum(II)–amine complexes containing bis(aminopropyl)dicarba-closo-dodecaborane(12) ligands"", 《DALTON TRANS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008584A (en) * | 2016-06-01 | 2016-10-12 | 哈尔滨工业大学无锡新材料研究院 | Method for controlling carborane derivative structure by click reaction |
| CN109851810A (en) * | 2019-03-22 | 2019-06-07 | 浙江大学 | A kind of borane anion supermolecule organic framework materials and its preparation method and application |
| CN111471190A (en) * | 2020-05-21 | 2020-07-31 | 南京工业大学 | Covalent organic framework material with carborane as starting material and preparation method and application thereof |
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Application publication date: 20160504 |