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WO2014054955A1 - A method for preparing microporous mof materials - Google Patents

A method for preparing microporous mof materials Download PDF

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Publication number
WO2014054955A1
WO2014054955A1 PCT/PL2013/000129 PL2013000129W WO2014054955A1 WO 2014054955 A1 WO2014054955 A1 WO 2014054955A1 PL 2013000129 W PL2013000129 W PL 2013000129W WO 2014054955 A1 WO2014054955 A1 WO 2014054955A1
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formula
organic
group
grinding
organic solvent
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WO2014054955A4 (en
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Janusz Zbigniew LEWIŃSKI
Daniel PROCHOWICZ
Kamil SOKOŁOWSKI
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Politechnika Warszawska
Instytut Chemii Fizycznej of PAN
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Politechnika Warszawska
Instytut Chemii Fizycznej of PAN
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]

Definitions

  • the object of the invention is a method for the preparation of microporous MOF materials based on the [ZILJO] 6 * core.
  • Metal-organic frameworks are a class of hybrid materials that have attracted a considerable attention in recent years. These functional materials are useful for a wide variety of applications, such as catalysis, gas storage, selective gas separation, nonlinear optics, and in pharmacy or medicine.
  • MOFs have attracted worldwide attention in the area of hydrogen storage (which is a key issue in development of hydrogen-based economy) or other gases important for the industry i.e. CH 4 , C 2 H 2 , CO, C0 2 , H 2 S, freones and as such have been the subject of many scientific works and patent applications.
  • Another important direction of development in this field is the search for non-toxic matrices to stabilize, transport and controlled release of drugs inside the living organisms.
  • the strategy for the preparation of microporous hybrid inorganic-organic materials is based on the use of SBU (Secondary Builiding Units) that are composed of inorganic molecular or polyhedral structural entities and organic linkers.
  • SBU Secondary Builiding Unit
  • Zn-MOF materials based on secondary building unit (SBU) ⁇ Zn ⁇ O ⁇ 6 and the organic carboxylate linker are particularly intensely investigated.
  • MOF-5 is a prototypical metal-organic framework the structure of which consists of metal clusters [Zn 4 0(C0 2 ) ] joined by benzene dicarboxylate (BDC) linkers to form an extended 3D simple cubic topology.
  • BDC benzene dicarboxylate
  • the object of the invention is a method for the preparation microporous MOF material based on [Zn_(0] 6+ core by mechanical grinding.
  • the method of production of microporous MOF-type materials according to the invention is characterized in that in the presence of an organic linker a mechanic force is applied to molecular oxozinc precursors of the formula L ⁇ r ⁇ O, where ligand L stands for monoanion derived from carboxylic acid, primary or secondary amide of a carboxylic acid, imide, carbamate, diester of phosphoric acid (V), and as organic linker is used an organic ligand containing two or three carboxylic groups and possibly substituted with a functional group from the list: -F, -CI, -Br, -I, -OH, -CN, - N0 2 , -NH 2 , -SH, -CF 3 , ether group, linear or branched alkyl CI -CIO group, individually or in a mixture.
  • organic linker an organic ligand containing two or three carboxylic groups and possibly substituted with a functional group from the list: -F, -CI
  • the ligand L is a monoanion organic compound of formula 1 or of formula 2 or of formula 3 or of formula 4 or of formula 5 or of formula 6:
  • Ri, R 2; R 3 stand for hydrogen atom or linear or branched alkyl CI -CIO group possibly substituted with functional group selected from: -F, -CI, -Br, -I, -OH, -NH 2 , - SH, -CF 3 , ether group or aryl group possibly substituted with functional group selected from: -F, -CI, -Br, -I, -OH, -NH 2 , -SH, -CF 3 , ether group, wherein CI, C2, C3, C4, C5, C6 are carbon atoms attached to a hydrogen, linear or branched alkyl Cl- C10 group, aryl group possibly substituted with functional group selected from: -F, - CI, -Br, -I, -OH, -NH 2 , -SH, -CF 3 , ether group, linear or branched alkyl CI -CIO group, phenyl group.
  • the organic linker is a organic compound of formula 7 or of formula 8 or of formula 9 or of formula 10 or of formula 11 or of formula 12 or of formula 13 or of formula 14 or of formula 15.
  • R l s R 2 , R 3 , R 4 stand for hydrogen atom or linear or branched alkyl CI -CIO group or functional group selected from: -F, -CI, -Br, -I, -CN, -OH, -NH 2 , -SH, -CF 3 , -N0 2 , ether group.
  • the method of the invention allows for transformation of oxozinc precursor with corresponding bi- or multifunctional organic linkers or the mixture of various organic linkers in solid state by grinding.
  • the grinding is performed by the use of mortar and pestle, more preferably in a ball mill grinder.
  • the grinding is performed by the use of ball mill grinder in the frequency range of 5-50 Hz, more preferably 15-30 Hz.
  • the solid-state reaction is provided by neat grinding or in the presence of catalytic amounts of organic solvent.
  • the organic solvent is added in such an amount so that the value of ⁇ is in the range of 0 ⁇ y ⁇ 2.
  • the organic solvent is dimethylformamide, diethylformamide, N- methyl-2-pyrrolidone.
  • the grinding is conducted in the time range of 1 min - 2h, more preferably 1 min - lh.
  • the resulting microporous material is washed in order to remove the organic ligands from post-reaction mixture.
  • the solvent is chloroform, dichloromethane, tetrahydrofurane, dimethylformamide, diethylformamide, N-methyl-2-pyrrolidone or a mixture of these compounds.
  • the organic ligand is washed once, more preferably twice, most preferably 3-5 fold.
  • the resulting microporous material is recrystallized in a hot organic solvent after washing.
  • such activated material is heated in order to remove residual solvent in the temperature range of 25-300°C, more preferably 25-150°C.
  • the method of the invention allows for the preparation microporous MOF materials based on [Zn 4 0] 6+ core by mechanical grinding without or with small amount of solvent.
  • the use of molecular oxozinc precursors allows in this case to eliminate all of the inconveniences related to the solvothermal method of the synthesis of the MOF-type materials, such as: i) long reaction times ii) contamination with inorganic salts, iii) necessity of using high temperature. Simultaneously the simplicity of the work-up and especially the efficient washing of the organic ligand allows for the facile synthesis of pure porous materials for further use.
  • Compounds obtained according to the method of the invention are characterized by particle size in the range of 20nm - 5 ⁇ depending on the process conditions (type of precursor, reaction time, frequency, grinding and recrystallization methods).
  • the method of the invention provides a faster and more efficient route to the synthesis of model MOF materials based on core as well as novel MOFs materials inaccessible by conventional solution methods.
  • the utilization of the mixture of organic linkers allows for the preparation of original MC-MOF materials (Mixed-Component Metal-Organic Framework) with potentially better properties (eg. gas sorption).
  • Example 1 The method of the invention is presented in more detail in the following examples.
  • Example 1 The method of the invention is presented in more detail in the following examples.
  • Oxozinc precursor [Zri40(HNOCPh)6] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1 pattern (lower curve), as shown in Fig.l.
  • Example 2 Example 2
  • Oxozinc precursor [ZmC HNOCPh ⁇ ] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 15 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
  • Oxozinc precursor [ZmO HNOCPh),;] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added.
  • the as-synthesized grinded material was washed with chloroform (3-fold) and recrystallized from chloroform at 50°C for 24 h and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
  • Oxozinc precursor [Zn 4 0(HNOCC 2 H 5 ) 6 ] (0.07g, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF- 1.
  • Oxozinc precursor [Zn 4 0(C 4 H 8 NO) 6 ] (0.08g, 0.1 mmol) (where C 4 H 8 NO is a monoanion of N-methylopropionamide) and terephthalic acid (BDC) (0.050 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
  • Oxozinc precursor [Zn 4 0(0 2 CC 2 H 5 ) 6 ] (0.07g, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar in the presence of ⁇ DEF and shaken with a mixer mill (a ball mill grinder) for 1 h at an oscillation rate of 30 Hz.
  • the as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-l .
  • Oxozinc precursor [Zn 4 0(C 4 H 4 N0 2 ) 6 ] (0.08g, 0.1 mmol) (where C 4 H N0 2 is a monoanion of succinimide) and terephthalic acid (BDC) (0.046 g, 0.3 mmol) was placed in a steel jar in the presence of 50 ⁇ DEF and shaken with a mixer mill (a ball mill grinder) for 60 minutes at an oscillation rate of 30 Hz.
  • the as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
  • Oxozinc precursor [Zn 0(C 8 H 5 N0 2 ) 6 ] (0.1 lg, 0.1 mmol) (where C 8 H 5 N0 2 is a monoanion of phthalimde) and terephthalic acid (BDC) (0.047 g, 0.3 mmol) was placed in a steel jar in the presence of 50 ⁇ DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz.
  • the as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
  • Oxozinc precursor [ZrnOiC ⁇ HuO ⁇ ) ⁇ (0.17g, 0.1 mmol) (where C 12 Hn0 4 P is a monoanion of diphenylophosphate (V)) and terephthalic acid (BDC) (0.048 g, 0.3 mmol) was placed in a steel jar in the presence of ⁇ , DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz.
  • the as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
  • Oxozinc precursor [Zri 4 0(HNOCPh)6] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a mortar and grinded for 10 minutes. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
  • Oxozinc precursor [Zr ⁇ OiFFNOCPh ⁇ ] (O.lg, 0.1 mmol) and 2-aminoterephthalic acid (NH 2 bdc) (0.054g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern (lower curve), as shown in Fig.2.
  • Oxozinc precursor (0.14g, 0.1 mmol) (where C 13 Hi 0 NO is a monoanion of benzanilide) and 2-aminoterephthalic acid (NH 2 bdc) (0.052g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern.
  • Oxozinc precursor [Zn 0(OOCPh) ] (O.lg, 0.1 mmol) and 2-aminoterephthalic acid (NH 2 bdc) (0.053g, 0.3 mmol) was placed in a steel jar in the presence of 50 ⁇ > DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz.
  • the as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern.
  • Oxozinc precursor [Zn 4 0(C 8 H 5 N0 2 ) 6 ] (0.1 lg, 0.1 mmol) (where C 8 H N0 2 is a monoanion of phthalimide) and 2-aminoterephthalic acid (NH 2 bdc) (0.052g, 0.3 mmol) was placed in a steel jar in the presence of 50 ⁇ DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz.
  • the as- synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern.
  • Oxozinc precursor [Zn 4 0(HNOCPh) ] (O.lg, 0.1 mmol) and 2,6- naphthalenedicarboxylic acid (NDC) (0.065g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added.
  • the as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum.
  • the as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-8 pattern (lower curve), as was shown in Fig.3.
  • Oxozinc precursor [Zn 4 0(OOCPh) 6 ] (O.lg, 0.1 mmol) and 2,6- naphthalenedicarboxylic acid (NDC) (0.063g, 0.3 mmol) was placed in a steel jar in the presence of 50 ⁇ DEF and shaken with a mixer mill (a ball mill grinder) for 60 minutes at an oscillation rate of 30 Hz.
  • the as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum.
  • the as- prepared material showed a PXRD pattern consistent with the calculated IRMOF-8 pattern.
  • Oxozinc precursor [Zr ⁇ OiTNiHOCPh ⁇ ] (O.lg, 0.1 mmol) and terephthalic acid (0.016 g, 0.1 mmol), 2-bromoterephthalic acid (0.024 g, 0.1 mmol), 2-aminoterephthalic acid (0.018 g, 0.1 mmol) was placed in a steel jar in the presence of 50 ⁇ _, DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The PXRD pattern of as-prepared material is shown in Fig.4. The BET surface area is calculated to be 1200 m 2 /g.

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Description

A method for preparing microporous MOF materials
The object of the invention is a method for the preparation of microporous MOF materials based on the [ZILJO]6* core.
Metal-organic frameworks (MOFs) are a class of hybrid materials that have attracted a considerable attention in recent years. These functional materials are useful for a wide variety of applications, such as catalysis, gas storage, selective gas separation, nonlinear optics, and in pharmacy or medicine. In particular, MOFs have attracted worldwide attention in the area of hydrogen storage (which is a key issue in development of hydrogen-based economy) or other gases important for the industry i.e. CH4, C2H2, CO, C02, H2S, freones and as such have been the subject of many scientific works and patent applications. Another important direction of development in this field is the search for non-toxic matrices to stabilize, transport and controlled release of drugs inside the living organisms.
The strategy for the preparation of microporous hybrid inorganic-organic materials is based on the use of SBU (Secondary Builiding Units) that are composed of inorganic molecular or polyhedral structural entities and organic linkers. Among them, Zn-MOF materials based on secondary building unit (SBU) {Zn^O}6 and the organic carboxylate linker are particularly intensely investigated. MOF-5 is a prototypical metal-organic framework the structure of which consists of metal clusters [Zn40(C02) ] joined by benzene dicarboxylate (BDC) linkers to form an extended 3D simple cubic topology. The most popular synthetic method of obtaining MOFs utilizes solvothermal conditions. This method requires the synthesis to be carried out in the presence of an organic solvent and at high temperature (up to 130°C or more) for a relatively long time (from over a dozen hours to several days). General information on the synthesis of a series of MOF materials is reported in a number of publications, including Yaghi et al., Nature 402 (1999) 276-279; B. Chen, M. Eddaoudi, Yaghi et al. Science 291 (2001) 1021-1023; Yaghi et al, Science 295
(2002) 469-472; Yaghi et al., Nature 423 (2003) 705-714; Yaghi et al., Science 300
(2003) 1127-1129.
The synthetic procedure described in US patent No. 2003/0004364 involves the use of inorganic zinc salt [Ζη(Ν03)2·6Η20] as a precursor of the [ZruO]6* core and a ditopic carboxylate acid as organic linker dissolved in a solvent. The product is then crystallized by slowly diffusing a diluted base solution into the post-reaction mixture solution to initiate the crystallization or by transferring the solution to a closed vessel and heating to a predetermined high temperature (solvothermal method).
Another method (Huang, L.; Wang, H.; Chen, J.; Wang, Z.; Sun, J.; Zhao, D.; Yan, Y. Microporous Mesoporous Mater. 2003, 58, 105) involves the use of [Ζη(Ν03)2·6Η20], the corresponding ditopic carboxylate acid and an amine in an organic solvent, and stirring such mixture for several hours at room temperature. Alternatively, a zinc salt Zn(CH3COO)2-2H20 may be used as a precursor of the [Zri40]6+ core. ( D. J. Tranchemontagne, J. R. Hunt, O. M. Yaghi, Tetrahedron, 2008, 64, 8553). The mentioned examples as well as the subsequent studies have shown that the physicochemical properties of MOF materials depend largely on the synthetic procedure (reaction conditions, substrates, solvents) and the purification methods. [S. S. Kaye, A. Dailly, O. M. Yaghi, J. R. Long, J. Am. Chem. Soc., 2007, 129, 14176; J. Hafizovic, M. Bjorgen, U. Olsbye, P. D. C. Dietzel, S. Bordiga, C. Prestipino, C. Lamberti, K. P. Lillerud, J. Am. Chem. Soc, 2007, 129, 3612]. Moreover, the use of the mentioned method often generates the impurities (inorganic metal salts) in the pores of the resulted materials, which adversely affects the sorption properties.
Recently, the BASF company has developed and commercialized the synthesis of microporous MOF materials on an industrial scale. (U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastre, J. Mater. Chem. 2006, 16 626). In this context, much attention has been paid to the development of new energy-efficient, economical and environmentally friendly synthesis methods of MOF materials. In US patent No. 2009/0131643, the microwave-assisted processes have been used to produce MOF materials. Such processes can significantly increase the speed and yield of the chemical reactions. The synthesis of MOFs can be achieved within a short time ranging from 5 seconds to a few minutes. However, it is still necessary to add organic solvent to the reagents mixture.
In the research work [S. Hausdorf, F. Baitalow, T. Bohle, D. Rafaja, F. O. R. L. Mertens, J. Am. Chem. Soc. 2010, 132, 10978-10981] instead of inorganic salt as a precursor of the [Zn.tO]6+ core, oxozinc clusters of the formula [Zri40(02CR)6] (where R = monocarboxylic acid) were used in a controlled reaction with dicarboxylic acid in the presence of organic solvent to obtain the corresponding microporous MOF material. To sum up, all the above examples of synthetic procedure for preparation MOF materials require elevated temperature, presence of solvent and generate difficult to remove impurities. Therefore, the development of new, rational and environmentally friendly methods for MOF synthesis with desired physical and chemical properties is now one of the most challenging tasks for chemists. The recent literature reports indicate that the mechanochemistry is a very efficient method of synthesis of complex materials as a result of a direct reaction between reagents in solid state by use of mechanic force, avoiding the use of solvent (as in neat grinding), or reducing the amount of solvent to catalytic or near stoichiometric amounts (e.g. in Liquid-Assisted Grinding, LAG). The small amount of liquid present in the reaction makes LAG reactivity distinct from neat mechanosynthesis or solution synthesis.
The patent application US2009/0143595 describes the mechanochemical method for the preparation of MOF materials by grinding transition metal salts MX2 wherein X2= (Oac)2, (HC03)2, (F3CC02)2, (acac)2, (F6acac)2, (N03)2) with corresponding organic ligands. To empirically distinguish between these liquid- assisted methods the parameter rj was introduced, which corresponds to the ratio of the liquid phase [μί] to the amount of solid reactants[mg].[T. Friscic, S. L. Childs, S. A. A. Rizvi, W. Jones CrystEngComm, 2009, 11, 418-426] Value of η = 0 refers to a mechanochemical reaction without the use of a solvent, the value of rj > 12 describes a typical synthesis in a solvent.
However, according to US2009/0143595 patent there are no reports on the mechanosynthesis of MOF materials based on the [Zr^O]6* core while the use of molecular oxozinc precursors LeZr^O in mechanochemical reaction with appropriate carboxylic acids allows obtaining microporous materials with [Zri40]6+ core in high yields and high purity.
The object of the invention is a method for the preparation microporous MOF material based on [Zn_(0]6+ core by mechanical grinding.
The method of production of microporous MOF-type materials according to the invention is characterized in that in the presence of an organic linker a mechanic force is applied to molecular oxozinc precursors of the formula L^r^O, where ligand L stands for monoanion derived from carboxylic acid, primary or secondary amide of a carboxylic acid, imide, carbamate, diester of phosphoric acid (V), and as organic linker is used an organic ligand containing two or three carboxylic groups and possibly substituted with a functional group from the list: -F, -CI, -Br, -I, -OH, -CN, - N02, -NH2, -SH, -CF3, ether group, linear or branched alkyl CI -CIO group, individually or in a mixture.
Preferably, the ligand L is a monoanion organic compound of formula 1 or of formula 2 or of formula 3 or of formula 4 or of formula 5 or of formula 6:
Figure imgf000005_0001
formula 1
Figure imgf000005_0002
formula 2
Figure imgf000005_0003
formula 3
Figure imgf000005_0004
formula 4
Figure imgf000005_0005
formula 5
O
I I
I R 2
o
I
R ,
formula 6 wherein Ri, R2; R3 stand for hydrogen atom or linear or branched alkyl CI -CIO group possibly substituted with functional group selected from: -F, -CI, -Br, -I, -OH, -NH2, - SH, -CF3, ether group or aryl group possibly substituted with functional group selected from: -F, -CI, -Br, -I, -OH, -NH2, -SH, -CF3, ether group, wherein CI, C2, C3, C4, C5, C6 are carbon atoms attached to a hydrogen, linear or branched alkyl Cl- C10 group, aryl group possibly substituted with functional group selected from: -F, - CI, -Br, -I, -OH, -NH2, -SH, -CF3, ether group, linear or branched alkyl CI -CIO group, phenyl group.
Preferably, the organic linker is a organic compound of formula 7 or of formula 8 or of formula 9 or of formula 10 or of formula 11 or of formula 12 or of formula 13 or of formula 14 or of formula 15.
Figure imgf000006_0001
formula 7
Figure imgf000006_0002
formula 8
Figure imgf000006_0003
formula 9
formula 10
Figure imgf000007_0001
formula 12
Figure imgf000007_0002
formula 13
formula 14
Figure imgf000008_0001
formula 15 wherein Rl s R2, R3, R4 stand for hydrogen atom or linear or branched alkyl CI -CIO group or functional group selected from: -F, -CI, -Br, -I, -CN, -OH, -NH2, -SH, -CF3, -N02, ether group.
The method of the invention allows for transformation of oxozinc precursor with corresponding bi- or multifunctional organic linkers or the mixture of various organic linkers in solid state by grinding.
Preferably, the grinding is performed by the use of mortar and pestle, more preferably in a ball mill grinder.
Preferably, the grinding is performed by the use of ball mill grinder in the frequency range of 5-50 Hz, more preferably 15-30 Hz.
Preferably, the solid-state reaction is provided by neat grinding or in the presence of catalytic amounts of organic solvent.
Preferably, the organic solvent is added in such an amount so that the value of η is in the range of 0<y<2.
Preferably, the organic solvent is dimethylformamide, diethylformamide, N- methyl-2-pyrrolidone.
Preferably, the grinding is conducted in the time range of 1 min - 2h, more preferably 1 min - lh.
Preferably, the resulting microporous material is washed in order to remove the organic ligands from post-reaction mixture.
Preferably, the solvent is chloroform, dichloromethane, tetrahydrofurane, dimethylformamide, diethylformamide, N-methyl-2-pyrrolidone or a mixture of these compounds. Preferably, the organic ligand is washed once, more preferably twice, most preferably 3-5 fold.
Preferably, the resulting microporous material is recrystallized in a hot organic solvent after washing.
Preferably, such activated material is heated in order to remove residual solvent in the temperature range of 25-300°C, more preferably 25-150°C.
The method of the invention allows for the preparation microporous MOF materials based on [Zn40]6+ core by mechanical grinding without or with small amount of solvent. The use of molecular oxozinc precursors allows in this case to eliminate all of the inconveniences related to the solvothermal method of the synthesis of the MOF-type materials, such as: i) long reaction times ii) contamination with inorganic salts, iii) necessity of using high temperature. Simultaneously the simplicity of the work-up and especially the efficient washing of the organic ligand allows for the facile synthesis of pure porous materials for further use.
Compounds obtained according to the method of the invention are characterized by particle size in the range of 20nm - 5μιη depending on the process conditions (type of precursor, reaction time, frequency, grinding and recrystallization methods). The method of the invention provides a faster and more efficient route to the synthesis of model MOF materials based on
Figure imgf000009_0001
core as well as novel MOFs materials inaccessible by conventional solution methods. In addition, the utilization of the mixture of organic linkers allows for the preparation of original MC-MOF materials (Mixed-Component Metal-Organic Framework) with potentially better properties (eg. gas sorption).
The method of the invention is presented in more detail in the following examples. Example 1
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1)
Oxozinc precursor [Zri40(HNOCPh)6] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1 pattern (lower curve), as shown in Fig.l. Example 2
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1) Oxozinc precursor [ZmC HNOCPh^] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 15 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 3
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1)
Oxozinc precursor [ZmO HNOCPh),;] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3-fold) and recrystallized from chloroform at 50°C for 24 h and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 4
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1)
Oxozinc precursor [Zn40(HNOCC2H5)6] (0.07g, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF- 1.
Example 5
Preparation of microporous material of formula ZaiO(BDC)3 (IRMOF-1)
Oxozinc precursor [Zn40(C4H8NO)6] (0.08g, 0.1 mmol) (where C4H8NO is a monoanion of N-methylopropionamide) and terephthalic acid (BDC) (0.050 g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 6
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1) Oxozinc precursor [Zn40(02CPh)6] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.050 g, 0.3 mmol) was placed in a steel jar in the presence of ΙΟΟμί DEF and shaken with a mixer mill (a ball mill grinder) for 1 h at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 7
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1)
Oxozinc precursor [Zn40(02CC2H5)6] (0.07g, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a steel jar in the presence of ΙΟΟμί DEF and shaken with a mixer mill (a ball mill grinder) for 1 h at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-l .
Example 8
Preparation of microporous material of formula Zri40(BDC)3 (IRMOF-1)
Oxozinc precursor [Zn40(C4H4N02)6] (0.08g, 0.1 mmol) (where C4H N02 is a monoanion of succinimide) and terephthalic acid (BDC) (0.046 g, 0.3 mmol) was placed in a steel jar in the presence of 50μΕ DEF and shaken with a mixer mill (a ball mill grinder) for 60 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 9
Preparation of microporous material of formula Zri40(BDC)3 (IRMOF-1)
Oxozinc precursor [Zn 0(C8H5N02)6] (0.1 lg, 0.1 mmol) (where C8H5N02 is a monoanion of phthalimde) and terephthalic acid (BDC) (0.047 g, 0.3 mmol) was placed in a steel jar in the presence of 50μΕ DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 10
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1) Oxozinc precursor [Zn40(C17H14N02)6] (0.18g, 0.1 mmol) (where C17Hi4N02 is a monoanion of dibenzylamine carbamate) and terephthalic acid (BDC) (0.048 g, 0.3 mmol) was placed in a steel jar in the presence of 50μί DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 1 1
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1)
Oxozinc precursor [ZrnOiC^HuO^)^ (0.17g, 0.1 mmol) (where C12Hn04P is a monoanion of diphenylophosphate (V)) and terephthalic acid (BDC) (0.048 g, 0.3 mmol) was placed in a steel jar in the presence of ΙΟΟμΙ, DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 12
Preparation of microporous material of formula Zn40(BDC)3 (IRMOF-1)
Oxozinc precursor [Zri40(HNOCPh)6] (O.lg, 0.1 mmol) and terephthalic acid (BDC) (0.049 g, 0.3 mmol) was placed in a mortar and grinded for 10 minutes. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-1.
Example 13
Preparation of microporous material of formula Zn40(NH2bdc)3 (IRMOF-3)
Oxozinc precursor [Zr^OiFFNOCPh^] (O.lg, 0.1 mmol) and 2-aminoterephthalic acid (NH2bdc) (0.054g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern (lower curve), as shown in Fig.2. Example 14
Preparation of microporous material of formula Zn40(NH2bdc)3 (IRMOF-3) Oxozinc precursor
Figure imgf000013_0001
(0.14g, 0.1 mmol) (where C13Hi0NO is a monoanion of benzanilide) and 2-aminoterephthalic acid (NH2bdc) (0.052g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern.
Example 15
Preparation of microporous material of formula Zn40(NH2bdc)3 (IRMOF-3)
Oxozinc precursor [Zn 0(OOCPh) ] (O.lg, 0.1 mmol) and 2-aminoterephthalic acid (NH2bdc) (0.053g, 0.3 mmol) was placed in a steel jar in the presence of 50μΙ> DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern.
Example 16
Preparation of microporous material of formula Zn40(NH2bdc)3 (IRMOF-3)
Oxozinc precursor [Zn40(C8H5N02)6] (0.1 lg, 0.1 mmol) (where C8H N02 is a monoanion of phthalimide) and 2-aminoterephthalic acid (NH2bdc) (0.052g, 0.3 mmol) was placed in a steel jar in the presence of 50μί DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. The as- synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-3 pattern.
Example 17
Preparation of microporous material of formula Zn40(NDC)3 (IRMOF-8)
Oxozinc precursor [Zn40(HNOCPh) ] (O.lg, 0.1 mmol) and 2,6- naphthalenedicarboxylic acid (NDC) (0.065g, 0.3 mmol) was placed in a steel jar and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. No solvent was added. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The as-prepared material showed a PXRD pattern consistent with the calculated IRMOF-8 pattern (lower curve), as was shown in Fig.3.
Example 18 Preparation of microporous material of formula Zn40(NDC)3 (IRMOF-8)
Oxozinc precursor [Zn40(OOCPh)6] (O.lg, 0.1 mmol) and 2,6- naphthalenedicarboxylic acid (NDC) (0.063g, 0.3 mmol) was placed in a steel jar in the presence of 50μί DEF and shaken with a mixer mill (a ball mill grinder) for 60 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3-fold) and subsequently dried under vacuum. The as- prepared material showed a PXRD pattern consistent with the calculated IRMOF-8 pattern.
Example 19
Preparation of MC-MOF material (Mixed-Component Metal-Organic Framework) Oxozinc precursor [Zr^OiTNiHOCPh^] (O.lg, 0.1 mmol) and terephthalic acid (0.016 g, 0.1 mmol), 2-bromoterephthalic acid (0.024 g, 0.1 mmol), 2-aminoterephthalic acid (0.018 g, 0.1 mmol) was placed in a steel jar in the presence of 50μΙ_, DEF and shaken with a mixer mill (a ball mill grinder) for 30 minutes at an oscillation rate of 30 Hz. The as-synthesized grinded material was washed with chloroform (3 -fold) and subsequently dried under vacuum. The PXRD pattern of as-prepared material is shown in Fig.4. The BET surface area is calculated to be 1200 m2/g.

Claims

Claims
1. Method for preparation microporous MOF material based on [Zn40]6+ core characterized in that in the presence of an organic linker or the mixture of various linkers a mechanic force is applied to molecular oxozinc precursors of the formula L6Zii40, where ligand L stands for monoanion derived from carboxylic acid, primary or secondary amide of a carboxylic acid, imide, carbamate, diester of phosphoric acid (V), and as organic linker is used an organic ligand containing two or three carboxylic groups and possibly substituted with a functional group from the list: -F, -CI, -Br, -I, -OH, -CN, -N02, -NH2, -SH, -CF3, ether group, linear or branched alkyl CI -CIO group.
2. Method as claimed in Claim 1, characterized in that ligand L is a monoanionic organic compound of formula 1 or of formula 2 or of formula 3 or of formula 4 or of formula 5 or of formula 6:
Figure imgf000015_0001
formula 1
Figure imgf000015_0002
formula 2
Figure imgf000015_0003
formula 3
Figure imgf000015_0004
formula 4
Figure imgf000016_0001
formula 5
O
II
HO-P-C
I
o
I
R ,
formula 6 wherein R1; R2, R3 stand for hydrogen atom or linear or branched CI -CIO alkyl group possibly substituted with functional group selected from: -F, -CI, -Br, -I, - OH, -NH2, -SH, -CF3, ether group or aryl group possibly substituted with functional group selected from: -F, -CI, -Br, -I, -OH, -NH2, -SH, -CF3, ether group, wherein CI, C2, C3, C4, C5, C6 stand for carbon atom attached to a hydrogen, linear or branched CI -CIO alkyl group, aryl group possibly substituted with functional group selected from: -F, -CI, -Br, -I, -OH, -NH2, -SH, -CF3, ether group, linear or branched CI -CI O alkyl group, phenyl group.
3. Method as claimed in Claim 1, characterized in that the organic linker is an organic compound of formula 7 or of formula 8 or of formula 9 or of formula 10 or of formula 11 or of formula 12 or of formula 13 or of formula 14 or of formula 15.
Figure imgf000016_0002
formula 7
Figure imgf000016_0003
formula 8
Figure imgf000017_0001
formula 9
Figure imgf000017_0002
formula 10
Figure imgf000017_0003
formula 11
Figure imgf000017_0004
formula 12
Figure imgf000017_0005
formula 13
Figure imgf000018_0001
formula 15 wherein Rl5 R2, R3, R4 stand for hydrogen atom or linear or branched CI -CIO alkyl group or functional group selected from: -F, -CI, -Br, -I, -CN, -OH, -NH2, -SH, - CF3, -N02, ether group.
4. Method as claimed in Claim 1, characterized in that the reaction is conducted in solid state by grinding.
5. Method as claimed in Claim 4, characterized in that the grinding is provided by the use of mortar and pestle or a ball mill grinder.
6. Method as claimed in Claim 5, characterized in that the grinding is performed by the use of ball mill grinder in the frequency range of 15-30 Hz.
7. Method as claimed in Claim 4, characterized in that the solid-state reaction is provided by neat grinding or in the presence of small amounts of organic solvent.
8. Method as claimed in Claim 7, characterized in that the organic solvent is added in such an amount so that the value for η is in the range of 0<//<2.
9. Method as claimed in Claim 7 or 8, characterized in that the organic solvent is dimethylformamide, diethylformamide, N-methyl-2-pyrrolidone.
10. Method as claimed in Claim 1, characterized in that the grinding is conducted in the time range of 1 min - 2h.
11. Method as claimed in Claim 1, characterized in that the resulting microporous material is washed with organic solvent.
12. Method as claimed in Claim 1 1, characterized in that the organic solvent is chloroform, dichloromethane, tetrahydrofurane, dimethylformamide, diethylformamide, N-methyl-2-pyrrolidone or a mixture of these compounds.
13. Method as claimed in Claim 1, characterized in that the resulting microporous material after washing is recrystallized from a hot organic solvent.
14. Method as claimed in Claim 13, characterized in that such activated material is heated at the temperature range of 25-300°C.
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