ROZTOCKI KORNEL (PL)
SINGH A K ET AL: "Complexes of 3d metal ions of the Schiff-base, 4-hydroxy-N'-(4'-octadecyloxybenzylidene)benzohydrazide: Synthesis, spectral studies, crystal structure and magnetic interactions", POLYHEDRON, PERGAMON PRESS, OXFORD, GB, vol. 28, no. 13, 2 September 2009 (2009-09-02), pages 2599 - 2604, XP026468342, ISSN: 0277-5387, [retrieved on 20090527], DOI: 10.1016/J.POLY.2009.05.039
WEN-XIU NI ET AL: "In Situ Immobilization of Metalloligands: A Synthetic Route to Homometallic Mixed-Valence Coordination Polymers", INORGANIC CHEMISTRY, vol. 48, no. 4, 16 February 2009 (2009-02-16), pages 1433 - 1441, XP055212112, ISSN: 0020-1669, DOI: 10.1021/ic8015244
WEN-XIU NI ET AL: "pH-Induced formation of metalloligand: increasing structure dimensionality by tuning number of ligand functional sites", CHEMICAL COMMUNICATIONS, no. 33, 1 January 2007 (2007-01-01), pages 3479, XP055212116, ISSN: 1359-7345, DOI: 10.1039/b705603f
ZHAO Q H ET AL: "Synthesis, crystal structures and magnetic properties of a coordination polymer containing the [Mn5(mu1,1-N3)8(N3)2(bpd)5(H2O)2] repeat cluster units (bpd=1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene)", INORGANIC CHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 9, no. 7, 1 July 2006 (2006-07-01), pages 699 - 702, XP028039857, ISSN: 1387-7003, [retrieved on 20060701], DOI: 10.1016/J.INOCHE.2006.04.009
YAEL DISKIN-POSNER ET AL: "Supramolecular assembly of metalloporphyrins in crystals by axial coordination through amine ligands", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS, no. 19, 1 January 2001 (2001-01-01), pages 2775 - 2782, XP055212130, ISSN: 1472-7773, DOI: 10.1039/b104961p
| 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", so42". 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", SO42", 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", SO42", 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 and deprotonated terephthalic acid, as well as guest molecules contained in the pores, e.g. Ν,Ν'-dimethylformamide and water. 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)2χ4Η20, 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. |
The present invention relates to a new metalloligand of the formula [Mn(L) 2 (H 2 0)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 (H 2 0)4]X 2 and metal-organic frameworks (MOFs) constructed with its use.
A new metalloligand of the formula [Mn(L) 2 (H 2 0)4]X 2 according to the present invention comprises a Mn 2+ 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 N0 3 " , CI " ,
A method for the preparation of a new metalloligand of the formula [Mn(L) 2 (H 2 0)4]X 2 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 C 1-8 alcohols, aqueous solutions of C 1-8 alcohols, mixtures of water, C 1-8 alcohol and Ν,Ν'-dimethylformamide (DMF) or mixtures of water, C 1-8 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(N0 3 ) 2 ' 4H 2 0, 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(N0 3 ) 2 4H 2 0, 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 Mn 2+ and Zn 2+ 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 (H 2 0)4]X2 or a ligand L and Mn(X) 2 , preferably Mn(N0 3 ) 2 4H 2 0, are reacted with Zn(N0 3 ) 2 4H 2 0, 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 (H 2 0) 4 ]X 2 (1), where X= N0 3 "
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(N0 3 ) 2 4H 2 0 (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 C 24 H 28 Ni 0 Oi 2 Mn: 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) A 3 , T = 100(2) K, Z = 2, D c = 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; wR 2 = 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)2'4H 2 0 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, H 2 0, CHC1 3 , 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 C 85 H 97 Ni 5 0 34 Mn 2 Zn 4 : 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 N 2 adsorption isotherm (77K) for the activated network (220°C, 30 min).
Fig. 5. The H 2 adsorption isotherm (77K) for the activated network (220°C, 30 min).