WO2015194981A1 - New metalloligand, a metal-organic framework (mof) comprising thereof and a method for its preparation - Google Patents
New metalloligand, a metal-organic framework (mof) comprising thereof and a method for its preparation Download PDFInfo
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- WO2015194981A1 WO2015194981A1 PCT/PL2015/050024 PL2015050024W WO2015194981A1 WO 2015194981 A1 WO2015194981 A1 WO 2015194981A1 PL 2015050024 W PL2015050024 W PL 2015050024W WO 2015194981 A1 WO2015194981 A1 WO 2015194981A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic System
- C07F13/005—Compounds without a metal-carbon linkage
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Abstract
The disclosed invention relates to a new metalloligand of the formula [Mn(L)2(H2O)4]X2 and a method for its preparation and a metal-organic framework (MOF) constructed using the new metalloligand and a method for its preparation.
Description
New metalloligand, a metal-organic framework (MOF) comprising thereof and a method for its preparation
The present invention relates to a new metalloligand of the formula [Mn(L)2(H20)4]X2 and a method for its preparation and a metal-organic framework (MOF) constructed using the new metalloligand and a method for its preparation.
There are no literature reports on a metalloligand of the formula [Mn(L)2(H20)4]X2 and metal-organic frameworks (MOFs) constructed with its use.
A new metalloligand of the formula [Mn(L)2(H20)4]X2 according to the present invention comprises a Mn2+ cation, a neutral molecule of hydrazone (L), derived from isonicotinic acid hydrazide and 4-pyridinecarbaldehyde of the formula 1
(formula 1)
and an anion (X) compensating the positive charge of the Mn cation, selected from N03 ", CI",
A method for the preparation of a new metalloligand of the formula [Mn(L)2(H20)4]X2 according to the present invention is based on a one-step or two-step reaction. In the one-step reaction, isonicotinic acid hydrazide and 4-picolinic aldehyde are condensed in a solvent (Y), selected from C1-8 alcohols, aqueous solutions of C1-8 alcohols, mixtures of water, C1-8 alcohol and Ν,Ν'-dimethylformamide (DMF) or mixtures of water, C1-8 alcohol and Ν,Ν'- diethylformamide (DEF). Preferably, the reaction is conducted at a 1 : 1 molar ratio of the reactants. Subsequently, a manganese (II) salt of the general formula Mn(X)2, preferably Mn(N03)2 '4H20, preferably at a 1 :2 molar ratio of manganese (II) salt to hydrazone (L), in a solid form or dissolved in a solvent Y is added to the system.
In the two-step reaction, in the first step, a condensation of isonicotinic acid hydrazide and 4- picolinic aldehyde is conducted to isolate hydrazone L, preferably at a 1 : 1 molar ratio of the reactants, by mechanochemical means (without or with a small participation of a solvent, without or with the addition of 1-2 drops of sulfuric (VI) acid) or in a solvent Y. In the second step, a reaction of hydrazone in a solvent Y with a manganese (II) salt of the general formula
Mn(X)2, preferably Mn(N03)24H20, preferably at a 1 :2 molar ratio of manganese (II) salt to hydrazone (L), is conducted.
The one-step and two-step reactions in a solution are carried out within a temperature range from 0°C to 80°C.
The metal-organic framework (MOF) according to the present invention comprises Mn2+ and Zn2+ metal cations, an anion of hydrazone (L) derived from isonicotinic acid hydrazide and 4- picolinic aldehyde of the formula 2 and deprotonated terephthalic acid, as well as guest molecules contained in the pores, preferably Ν,Ν'-dimethylformamide and water.
(formula 2)
A method for the preparation of a metal-organic framework (MOF) according to the present invention consists in the fact that a metalloligand of the formula [Mn(L)2(H20)4]X2 or a ligand L and Mn(X)2, preferably Mn(N03)24H20, are reacted with Zn(N03)2 4H20, terephthalic acid and DMF under autogenous pressure, within a temperature range of 100-
180°C.
The invention has been described using the following embodiment.
Example 1 : Synthesis of [Mn(L)2(H20)4]X2 (1), where X= N03 "
Isonicotinic acid hydrazide (274 mg; 2.00 mmol) and 4-picolinic aldehyde (188 μΐ, 2.00 mmol) were introduced into approx. 92% ethanol (35 mL). The mixture was heated under a reflux condenser at the boiling point of EtOH for approximately 10 min. Mn(N03)24H20 (252 mg, 1.00 mmol) was dissolved separately in 5 mL of EtOH, introduced into the main solution, and the mixture was heated for 15 min. The resulting yellow solution was left to crystallize in an open vessel at room temperature. After 2 days, yellow crystals were obtained, which were filtered, washed with alcohol and air-dried. Yield: 546 mg, 77.6%. The product was identified using elemental, spectral and crystallographic analysis.
Elemental analysis: Measured: N, 19.68; C, 41.32; H, 4.02. Calculated for C24H28Ni0Oi2Mn: N, 19.91; C, 40.98; H, 4.01%. FT-IR (ATR, cm"1): v(C=0) 1674. Crystallographic data (SCXRD): monoclinic system, space group P 2i/c, a = 7.2250(10), b = 16.8390(3), c =
31.3100(2) A, V = 1545.68(4) A3, T = 100(2) K, Z = 2, Dc = 1.512 Mg m"3, μ = 0.505 mm"1, 12042 measured reflections, 3518 independent reflections, 3299 observed reflections [I > 2σ(7)]. Ri = 0.039; wR2 = 0.0844 [for 3299 observed reflections].
The resulting structure is presented in the drawing, wherein Fig. 1 represents its crystal structure without hydrogen atoms.
Example 2: Synthesis of a metal-organic framework (MOF)
174 mg (0.25 mmol) of the metalloligand obtained in Example 1, 1.88 mg (0.34 mmol) of Zn(N03)2'4H20 and 57 mg (0.33 mmol) of terephthalic acid were weighed, transferred to a glass autoclave reactor, and then 80 ml of DMF was added, and the mixture was dissolved using ultrasound (~2 min). The mixture was heated for 20 h at 160°C in the autoclave. The obtained yellow precipitate was filtered, washed with DMF and dried in a vacuum oven for 30 minutes at 60°C and under a pressure of 500 mbar. The weight of the resulting product was 120 mg. The product is a light yellow solid of a low bulk density, insoluble in such solvents as EtOH, H20, CHC13, acetone, DMF and DMSO, which indicates its polymeric structure. The product was identified using elemental, spectral, diffractometric and thermogravimetric analysis.
Elemental analysis: Measured: N, 8.46; C, 45.65; H, 4.37, calculated for C85H97Ni5034Mn2Zn4: N, 9.36; C, 45.49; H, 4.36%. FT-IR (ATR, cm"1): v(CH) 2931; v(C=0) 1664; v(COO) 1596, 1383.
Fig. 2. Powder diffraction pattern for metal-organic framework (MOF).
Fig. 3. Thermogravimetric curve for metal-organic framework (MOF).
Fig. 4. The N2 adsorption isotherm (77K) for the activated network (220°C, 30 min).
Fig. 5. The H2 adsorption isotherm (77K) for the activated network (220°C, 30 min).
Claims
1. A new metalloligand of the formula [Mn(L)2(H20)4]X2 comprising a Mn cation, a neutral molecule of hydrazone (L), derived from isonicotinic acid hydrazide and 4-picolinic aldehyde of the formula
and an anion (X) compensating the positive charge of the Mn cation.
2. A metalloligand according to claim 1, characterized in that the anion X is selected from
NO3 ", cr, cio4 ", so4 2".
3. A method for the preparation of a new metalloligand of the formula [Mn(L)2(H20)4]X2, characterized in that it is obtained as a result of a one-step or two-step reaction.
4. A method according to claim 3, characterized in that in the one-step reaction, isonicotinic acid hydrazide and 4-picolinic aldehyde are condensed in a solvent.
5. A method according to claim 4, characterized in that the solvent is selected from C1-8 alcohols, aqueous solutions of C1-8 alcohols, mixtures of water, C1-8 alcohol and Ν,Ν'- dimethylformamide (DMF) or mixtures of water, C1-8 alcohol and N,N'-diethylformamide
(DEF).
6. A method according to claim 4, characterized in that a manganese (II) salt is added to the system in its solid form or dissolved in a solvent.
7. A method according to claim 6, characterized in that a manganese (II) salt has the general formula Mn(X)2, wherein X is selected from N03 ", CI", CIO4 ", SO4 2", wherein the salt can be anhydrous or hydrated.
8. A method according to claim 6 or 7, characterized in that the manganese (II) salt is added to the resulting hydrazone (L) at a 1 :2 molar ratio.
9. A method according to claim 6, characterized in that the solvent is selected from C1-8 alcohols, aqueous solutions of C1-8 alcohols, mixtures of water, C1-8 alcohol and Ν,Ν'- dimethylformamide (DMF) or mixtures of water, C1-8 alcohol and N,N'-diethylformamide
(DEF).
10. A method according to claim 3, characterized in that in a two-step reaction, in the first step, a condensation of isonicotinic acid hydrazide and 4-picolinic aldehyde is conducted by mechanochemical means, without or with the small participation of a solvent.
11. A method according to claim 10, characterized in that the condensation reaction is conducted with the addition of 1-2 drops of sulfuric (VI) acid.
12. A method according to claim 3, characterized in that in a two-step reaction, in the first step, a condensation of isonicotinic acid hydrazide and 4-picolinic aldehyde is conducted in a solvent.
13. A method according to claim 12, characterized in that the solvent is selected from C1-8 alcohols, aqueous solutions of C1-8 alcohols, mixtures of water, C1-8 alcohol and Ν,Ν'- dimethylformamide (DMF) or mixtures of water, C1-8 alcohol and N,N'-diethylformamide
(DEF).
14. A method according to claim 10 or 11 or 12 or 13, characterized in that in the second step, a reaction of hydrazone in a solvent with a manganese (II) salt is conducted.
15. A method according to claim 14, characterized in that a manganese (II) salt has the general formula Mn(X)2, wherein X is selected from N03 ", CI", CIO4 ", SO4 2", wherein the salt can be anhydrous or hydrated.
16. A method according to claim 14 or 15, characterized in that the manganese (II) salt is added to the resulting hydrazone (L) at a 1 :2 molar ratio.
17. A method according to claim 14, characterized in that the solvent is selected from C1-8 alcohols, aqueous solutions of C1-8 alcohols, mixtures of water, C1-8 alcohol and Ν,Ν'- dimethylformamide (DMF) or mixtures of water, C1-8 alcohol and N,N'-diethylformamide
(DEF).
18. A method according to claim 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17, characterized in that the reactions are conducted within a temperature range from 0°C to 80°C.
19. A metal-organic framework (MOF) comprising Mn2+ and Zn2+ metal cations, an anion of hydrazone (L) derived from isonicotinic acid hydrazide and 4-picolinic aldehyde of the formula
20. A method for the preparation of a metal-organic framework (MOF), characterized in that a metalloligand of the formula [Mn(L)2(H20)4]X2 is reacted with Ζη(Ν03)2 χ4Η20, terephthalic acid and DMF.
21. A method for the preparation of a metal-organic framework (MOF), characterized in that the ligand L and Mn(X)2 are reacted with Zn(N03)2x4H20, terephthalic acid and DMF.
22. A method according to claim 21, characterized in that Mn(X)2 is Mn(N03)2 4H20.
23. A method according to claim 20 or 21 or 22, characterized in that the reaction is conducted using ultrasound in a sealed vessel under autogenous pressure within a temperature range of 100-180°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PLP.408588 | 2014-06-17 | ||
| PL408588A PL408588A1 (en) | 2014-06-17 | 2014-06-17 | New metal ligand with the formula [Mn(L)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]X<sub>2</sub> and method for obtaining it and the MOF network, built using the new metal ligand and method for obtaining it |
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| WO2015194981A1 true WO2015194981A1 (en) | 2015-12-23 |
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| PCT/PL2015/050024 WO2015194981A1 (en) | 2014-06-17 | 2015-06-17 | New metalloligand, a metal-organic framework (mof) comprising thereof and a method for its preparation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN109731611A (en) * | 2019-01-17 | 2019-05-10 | 中山大学 | A kind of composite material and preparation method and application based on Photoactive metal-organic coordination Molecular Ring and carbonitride |
| CN113461965A (en) * | 2021-08-10 | 2021-10-01 | 蚌埠医学院 | Novel metal organic framework compound and preparation method and application thereof |
| CN114196032A (en) * | 2021-10-22 | 2022-03-18 | 广东工业大学 | Tetrathiol functionalized UiO-66 type metal organic framework material and preparation method and application thereof |
-
2014
- 2014-06-17 PL PL408588A patent/PL408588A1/en unknown
-
2015
- 2015-06-17 WO PCT/PL2015/050024 patent/WO2015194981A1/en active Application Filing
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN109731611A (en) * | 2019-01-17 | 2019-05-10 | 中山大学 | A kind of composite material and preparation method and application based on Photoactive metal-organic coordination Molecular Ring and carbonitride |
| CN113461965A (en) * | 2021-08-10 | 2021-10-01 | 蚌埠医学院 | Novel metal organic framework compound and preparation method and application thereof |
| CN113461965B (en) * | 2021-08-10 | 2022-07-08 | 蚌埠医学院 | Novel metal organic framework compound and preparation method and application thereof |
| CN114196032A (en) * | 2021-10-22 | 2022-03-18 | 广东工业大学 | Tetrathiol functionalized UiO-66 type metal organic framework material and preparation method and application thereof |
| CN114196032B (en) * | 2021-10-22 | 2023-09-15 | 广东工业大学 | Tetrathiol functionalized UiO-66 type metal organic framework material and preparation method and application thereof |
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| PL408588A1 (en) | 2015-12-21 |
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