Metal-organic frameworks (MOFs), method for their preparation and their application

Abstract

Coordination polymers of MOF type, comprising a repeating unit of the general formula [M.sub.2(dcx).sub.2L.sub.2], wherein M represents a metal cation (M.sup.2+), dcx represents an anion of a dicarboxylic acid and L represents a neutral molecule of hydrazone. A method for preparation of coordination polymers of MOF type, wherein in the first step a compound of aldehyde or ketone group is condensed with a hydrazide, and in the second step the condensation product is reacted using a metal compound and a dicarboxylic acid. An application of coordination polymers of MOF type for the detection, capturing, separation, or storage of molecules, for the fabrication of ionic conductors, for the construction of batteries and fuel cells, as well as drug carriers.

Claims

1. A coordination polymer of MOF type, said coordination polymer comprises a repeating unit of the general formula [M.sub.2(dcx).sub.2L.sub.2], wherein M represents a metal cation (M.sup.2+); dcx represents an anion of a dicarboxylic acid; L represents a neutral molecule of hydrazone having two different functional groups CO and NH.

2. The coordination polymer of MOF type according to claim 1, wherein the metal cation is Zn.sup.2+, Cd.sup.2+, Cu.sup.2+, Mn.sup.2+, Co.sup.2+, or Ni.sup.2+.

3. The coordination polymer of MOF type according to claim 1, wherein dcx is an anion of an acid that is 1,4-benzenedicarboxylic acid (formula 1), substituted 1,4-benzenedicarboxylic acid (formula 2), 1,4-cyclohexanedicarboxylic acid (formula 3), 2,6-naphthalenedicarboxylic acid (formula 4), biphenyl-4,4-dicarboxylic acid (formula 5), thiophene-2,5-dicarboxylic acid (formula 6), or 2,5-dihydroxyterephthtalic acid (formula 7).

4. The coordination polymer of MOF type according to claim 1, wherein the hydrazone L is a compound of formula 8, 9 or 10: ##STR00006## wherein A, D, X, Z independently represent a nitrogen (N) atom, or a carbon atom with an amine substituent (CNH.sub.7), or a carbon atom with a hydrogen atom (CH), and wherein R represents a hydrogen atom, a C.sub.1-C.sub.6 alkyl or aryl group.

5. The coordination polymer of MOF type according to claim 1, wherein the coordination polymer further comprises one or more types of guest molecules.

6. The coordination polymer of MOF type according to claim 5, wherein the guest molecules are molecules of a solvent.

7. The coordination polymer of MOF type according to claim 6, wherein the molecules of the solvent is water, N,N-dimethylformamide, N,N-diethylformamide, or a C.sub.1-C.sub.8 alcohol.

8. The coordination polymer of MOF type according to claim 5, wherein the guest molecules are gas molecules.

9. The coordination polymer of MOF type according to claim 8, wherein the gas molecules are N.sub.2, H.sub.2, CO.sub.2, CO, Ar, NO, or NO.sub.2.

10. The coordination polymer of MOF type according to claim 8, wherein the gas molecules are C.sub.1-C.sub.6 alkanes, C.sub.2-C.sub.6 alkenes, C.sub.2-C.sub.6 alkynes, C.sub.6-C.sub.8 arenes, or C.sub.1-C.sub.8 alcohols.

11. The coordination polymer of MOF type according to claim 1, wherein said coordination polymer is in the absence of guest molecules.

12. A method for preparation of the coordination polymer of MOF type of claim 1, said method comprising in a first step forming a hydrazone L, a compound of aldehyde or ketone group that is condensed with a hydrazide to form a condensation product.

13. The method according to claim 12, further comprising in a second step reacting the condensation product with a metal compound and a dicarboxylic acid.

14. The method according to claim 13, wherein the metal compound is M(NO.sub.3).sub.2, M(ClO.sub.4).sub.2, M(SO.sub.4).sub.2, M(CH.sub.3COO).sub.2 or MCl.sub.2.

15. The method according to claim 13, wherein the dicarboxylic acid is 1,4-benzenedicarboxylic acid (formula 1), substituted 1,4-benzenedicarboxylic acid (formula 2), 1,4-cyclohexanedicarboxylic acid (formula 3), 2,6-naphthalenedicarboxylic acid (formula 4), biphenyl-4,4-dicarboxylic acid (formula 5), thiophene-2,5-dicarboxylic acid (formula 6), or 2,5-dihydroxyterephthtalic acid (formula 7).

16. The method according to claim 12, wherein the compound of aldehyde or ketone group is a compound of formula 11, 12 or 13: ##STR00007## wherein A and D independently represent a nitrogen (N) atom, a carbon atom with an amine substituent (CNH.sub.2), or a carbon atom with a hydrogen atom (CH), and R represents a hydrogen atom, a C.sub.1-C.sub.6 alkyl or aryl group condensed with a hydrazide.

17. The method according to claim 12, wherein the hydrazide is a compound of formula 14: ##STR00008## wherein X and Z independently represent a nitrogen (N) atom, a carbon atom with an amine substituent (CNH.sub.2), or a carbon atom with a hydrogen atom (CH).

18. The method according to claim 12, wherein the condensation reaction is conducted by mechanochemical means.

19. The method according to claim 18, wherein the condensation reaction is conducted with the addition of 1-2 drops of sulfuric (VI) acid.

20. The method according to claim 12, wherein the condensation reaction is conducted in a solvent.

21. The method according to claim 20, wherein the solvent is C.sub.1-C.sub.8 alcohol, an aqueous alcoholic solution, N,N-dimethylformamide (DMF), or N,N-diethylformamide (DEF).

22. The method according to claim 12, wherein the first step is conducted within a temperature range of from 20 C. to 150 C.

23. The method according to claim 12, wherein the first step is conducted under autogenous pressure, in a closed vessel.

24. An application of coordination polymers of MOF type of the general formula [M.sub.2(dcx).sub.2L.sub.2] according to claim 1, characterized in that the compounds are used for the detection, capturing, separation or storage of molecules, for the fabrication of ionic conductors, for the construction of batteries and fuel cells, as well as drug carriers.

25. An application according to claim 24, characterized in that the molecules are selected from water, carbon dioxide, carbon monoxide, alcohols, water, hydrocarbons.

26. An application according to claim 24, characterized in that the ionic conductors comprise ions selected from H.sup.+, Li.sup.+, Na.sup.+, IC, NH.sub.4.sup.+.

Description

EXAMPLE 1

(1) Synthesis of [M.sub.2(dcx).sub.2L.sub.2].G (product 1),

(2) wherein M.sup.2+=Zn.sup.2+; dcx=anion of 1,4-benzenedicarboxylic acid; L=hydrazone of the formula 8, wherein A=N; D=CH; X=N; Z=CH; R=H; G=1DMF.1H.sub.2O

(3) Step 1: Synthesis of hydrazone L:

(4) Isonicotinic acid hydrazide (686 mg; 5.00 mmol) was dissolved in 20 cm.sup.3 of ethanol. 4-picolinic aldehyde (0.471 cm.sup.3; 5.00 mmol) was added and the mixture was heated to reflux for 20 min. Subsequently the solution was left to cool and crystallize the product. After the crystallization the precipitate was filtered, and the filtrate was concentrated and left in ice bath until the crystallization of a further product fraction. The second crystallized fraction was filtered. The fractions were combined and air-dried. Yield: 1.02 g (90%). The synthesis and the X-ray structure of this hydrazone were described in the literature (W.-X. Ni, M. Li, X.-P. Zhou, Z. Li, X.-C. Huang, D. Li Chem. Commun. 2007, 3479).

(5) The compound was identified spectrally based on the selected bands:

(6) FT-IR (ATR, cm.sup.1): (CO).sub.L 1683, (NH) 3190.

(7) Step 2: Hydrazone L (453 mg; 2.00 mmol), 1,4-benzenedicarboxylic acid (332 mg; 2.00 mmol) and Zn(NO.sub.3).sub.2 were dissolved in 162 cm.sup.3 of N,N-dimethylformamide (DMF) and 18 cm.sup.3 of water. The sealed vessel was heated at 70 C. for 48 hours to yield a fine-crystalline yellow product (420 mg). The product was washed with DMF and dried in a vacuum oven (30 min, 60 C., 500 mbar). Yield: 42%.

(8) The product was identified using elemental, spectral, crystallographic, diffractometric and thermogravimetric analysis:

(9) Elemental analysis: Measured: N, 12.58; C, 49.80; H, 3.91. Calculated for C.sub.43H.sub.37N.sub.9O.sub.12Zn.sub.2: N, 12.57; C, 51.51; H, 3.72%.

(10) FT-IR (ATR, cm.sup.1): (COO).sub.as 1580, (COO).sub.s 1392, (CO).sub.DMF 1661, (CO).sub.L 1680, (NH) 3222.

(11) Crystallographic data (SCXRD): orthorhombic system, space group Iabc, a=15.1123(3), b=9.9069(3), c=31.2591(6) , V=9404.0(3) .sup.3, T=293(2) K, Z=8, D.sub.c=1.403 Mg m.sup.3, =1.082 mm.sup.1, 61329 measured reflections, 5813 independent reflections, 4390 observed reflections [I>2(I)]. R.sub.1=0.0724; wR.sub.2=0.1918 [for 4390 observed reflections].

(12) FIG. 1. PXRD powder diffraction pattern registered for product 1 (as). For comparison, a powder diffraction pattern calculated based on a single crystal SCXRD (calcd).

(13) FIG. 2. Thermogravimetric curve for product 1.

(14) Spatial structure of the obtained product 1 was illustrated in figures: FIG. 3, FIG. 4 and FIG. 5.

(15) FIG. 3. Fragment of the structure of product 1 illustrating the surrounding of Zn atoms (guest molecules and hydrogen atoms were skipped).

(16) FIG. 4. Fragment of the structure of product 1 demonstrating a double interpenetration of pillared-layered network (blue and orange) with Zn.sub.2 nodes-clusters forming layers with anions of a dicarboxylic acid dcx and hydrazone L, as a linker-pillar supporting the layers (guest molecules and hydrogen atoms were omitted).

(17) FIG. 5. Orthographic projection of the structure of product 1, illustrating the presence of one-dimensional channels, the double interpenetration of the network and the pillared-layered structure (guest molecules and hydrogen atoms were omitted).

EXAMPLE 2

(18) Synthesis of [M.sub.2(dcx).sub.2L.sub.2].G (product 2),

(19) wherein M.sup.2+=Zn.sup.2+; dcx=anion of 1,3-benzenedicarboxylic acid (formula XX below, X1=H);

(20) L=hydrazone of the formula 8, wherein A=N; D=CH; X=N; Z=CH; R=H; G=2DMF

(21) Step 1: Synthesis of hydrazone L:

(22) Isonicotinic acid hydrazide (686 mg; 5.00 mmol) was dissolved in 20 cm.sup.3 of ethanol. 4-picolinic aldehyde (0.471 cm.sup.3; 5.00 mmol) was added and the mixture was heated to reflux for 20 min. Subsequently the solution was left to cool and crystallize the product. After the crystallization the precipitate was filtered, and the filtrate was concentrated and left in ice bath until the crystallization of a further product fraction. The second crystallized fraction was filtered. The fractions were combined and air-dried. Yield: 1.02 g (90%). The synthesis and the X-ray structure of this hydrazone were described in the literature (W.-X. Ni, M. Li, X.-P. Zhou, Z. Li, X.-C. Huang, D. Li Chem. Commun. 2007, 3479).

(23) The compound was identified spectrally based on the selected bands:

(24) FT-IR (ATR, cm.sup.1): (CO).sub.L 1683, (NH) 3190.

(25) Step 2: Hydrazone L (36 mg; 0.16 mmol), 1,3-benzenedicarboxylic acid (27 mg; 0.16 mmol) and Zn(NO.sub.3).sub.2 (62 mg; 0.16 mmol) were dissolved in 16.2 cm.sup.3 of N,N-dimethylformamide (DMF) and 1.8 cm.sup.3 of water. The sealed vessel was heated at 60 C. for 70 hours to yield a fine-crystalline yellow product (20 mg). The product was washed with DMF and dried in a vacuum oven (30 min, 60 C., 500 mbar). Yield: 12%.

(26) The product was identified using elemental, spectral, crystallographic, diffractometric and thermogravimetric analysis:

(27) Elemental analysis: Measured: N, 13.21; C, 52.06; H, 4.19. Calculated for C.sub.46H.sub.44N.sub.10O.sub.12Zn.sub.2: N, 13.22; C, 52.14; H, 4.19%.

(28) FT-IR (ATR, cm.sup.1): (CO).sub.as 1557, (COO).sub.s 1394, (CO).sub.DMF 1685, (CO).sub.L 1675, (NH) 3208.

(29) ##STR00005##