Process for preparing porous organic framework materials

ES 2 349 337 T3

METHOD FOR THE PRODUCTION OF POROUS ORGANIC STRUCTURAL MATERIALS

DESCRIPTION

The present invention relates to a method for the production of porous organic framework materials.

Porous organic structural materials form an interesting category of substances that can be an alternative to inorganic zeolites for the most diverse applications.

Such applications are for example in the field of the retention, separation or controlled delivery of chemical substances, such as for example gases or in the field of catalysis. The porosity of the organic material plays a decisive role here in particular. Due to the defined pores present in the organic structural material, on the one hand, the specific surface of the material is increased and a selective separation of mixtures is made possible. The same is true for such materials when they are used in chemical reactions such as catalytic reactions.

A special group of these porous organic framework materials are the so-called organometallic framework materials. These are known in the state of the art and typically contain an organic compound at least bidentate linked in a coordinated manner to a metal ion. Such organometallic framework materials (MOF = organometallic frameworks) are described for example in US-A 5,648,508, EP-A 0 790 253, MO Keeffe, J. Sol. State Chem., 152 (2000), 3-20; H.Li et al., Nature 402 (1999), 276; M. Eddaoudi, Topics in catalysis 9 (1999), 105-111; B. Chen et al., Science 291 (2001), 1021-1023 and DE-A 101 11 230.

As a special group of these organometallic structural materials, the so-called limited structural materials are described in the most recent literature, in which the structure does not extend infinitely by means of the special choice of the organic compound but rather by the formation of polyhedra. AC Sudik, et al., J. Am. Chem. Soc. 127 (2005), 7110-7118, describe such special structural materials. Here this delimitation is mentioned as organometallic polyhedra (MOP = organometallic polyhedra).

Another modification of such porous organic framework materials represents the so-called covalent organic structures (COF = covalent organic structures). Here they are structural materials, in which in comparison with the organometallic structural materials the central metal atom has been replaced by an organic boron compound, those that preferably have changed at least two boron groups (RB (OH) 2, where R represents an organic radical). AP Coté, et al. Science 310 (2005), 1116-1170, describe for example such structural materials.

All of these organic structural materials have a common porosity. Closely linked with the porosity of such materials is the specific surface, which strongly influences their properties. As a measure of the characterization of such surfaces, the specific surface according to Langmuir is taken.

Hence, for the production of such materials, apart from good performance, the generation of high specific surfaces as well as reproducibility in production are also of great importance. This is particularly true for the production of large quantities of structural material.

For example, for organometallic framework materials such as MOF-5 (IRMOF-1), numerous synthesis methods are described in the literature.

Thus, for example H. Li, et al., Nature 402 (1999), 276-279 describe the synthesis of MOF-5 where a Langmuir surface of approximately 2900 m could be reached²/ g.

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In WO-A 02/070526, for example special solvents were used to produce MOF-5. This resulted in a specific surface area of ​​1063 m²/ g.

Also in WO-A 02/088148 different methods for the production of IRMOF-1 (MOF-5) are disclosed.

The production of MOF-5, in which a particularly high specific surface could be achieved, is described in WO-A 03/102000 as well as by JLC Rowsell, et al., J. Am. Chem. Soc. 126 (2004), 56665667.

All these literature citations show that in spite of basically the same reaction lines, porous organic framework materials are obtained which exhibit strongly different specific surfaces and thus can have different properties.

Hence there is a need to make available production methods which, in particular in the production of large quantities of porous organic framework materials, avoid the disadvantages described above.

Hence it is an object of the present invention to make available methods for the production of porous organic structural materials, which supply sufficiently large quantities of such structural materials, where these exhibit as high a specific surface as possible and can be produced with a high reproducibility.

The objective was achieved by means of a method for the production of a porous organometallic structural material, given the limited case, where it contains the stage:

Reaction of a reaction mixture in a liquid phase from at least one metallic compound with at least one organic compound at least bidentate, which can be bound to the metal in a coordinated manner, in the presence of a non-aqueous organic solvent in the presence and / or under liberation of water, where the organic compound exhibits at least two atoms chosen in each case independently of one another from the group consisting of oxygen, sulfur and nitrogen, on which the organic compound can be bound in a coordinated manner on the metal, characterized in that during the transformation the water is eliminated from the liquid phase of the reaction mixture.

In addition, the objective is solved by a method for the production of a porous boron-organic structural material, if limited, where it contains the stage:

Reaction of a liquid phase reaction mixture of at least one compound that exhibits at least two boron groups with at least one organic compound that has at least two functional groups, which can be covalently bonded on one group, in the presence of a non-aqueous organic solvent, where the organic compound having at least two functional groups exhibits at least two atoms chosen in each case independently of one another from the group consisting of oxygen, sulfur and nitrogen, on which the organic compound having two functional groups can be covalently bound to a boron group, characterized in that during the transformation water is removed from the liquid phase of the reaction mixture.

The surprising way was found that the porous organic structural materials described above (MOF, MOP, COF), in which a lower standard deviation is presented than that of the state of the art, can be materialized with comparatively high specific surfaces and values ​​with good reproducibility by removing water from the reaction mixture in the formation of the porous organic framework material.

In the case of organometallic structural materials, this water can be present in the reaction mixture in the form of water of crystallization of the metal compound. After the reaction of the

ES 2 349 337 T3 metal compound, the water of crystallization is no longer bound in a coordinated manner in the reaction mixture and can be eliminated from it. In addition, there is the possibility of using an organic solvent that is not totally anhydrous. Here too, the water present in the reaction mixture can therefore be removed. Finally, water can also form in the reaction. This applies for example then when the metal compound is present in the reaction mixture in the form of a metal hydroxide or a metal oxide and a reaction occurs with the at least bidentate organic compound, which can be for example an organic carboxylic acid. Here water is released by the formation of the metal complex compound. In this case, adding the metal compound to the reaction mixture as a hydroxide or as an oxide must be avoided. Rather, it can also be present in the form of a metal salt, where the hydroxide ions necessary for the formation of water can be generated by the formation of a base, such as caustic soda, or by means of the solvent.

In the case of boron organic framework materials, water is generated in particular by the reaction of boric acid with, for example, an alcohol.

The removal of water from the reaction mixture can take place in particular by distillation, by steam stripping or by adsorption agents. Suitable adsorption agents are, for example, aluminum oxide, silica gel or a molecular sieve, in particular a 3A or 4A molecular sieve.

In vapor entrainment (or so-called expulsion) components of this phase are removed from a liquid phase, by conducting gases over the liquid phase and are converted to a gaseous phase.

This is advantageous, among other things, when the reaction can take place under stirring, which is also advantageous in scaling-up. As a result, larger amounts of a desired porous organic make-up material can be obtained by reaction.

It is preferred that the reaction occurs at a pressure of maximum 2 bar (absolute). Furthermore, however preferably the pressure reaches a maximum of 1200 mbar (absolute). In particular the reaction preferably takes place at atmospheric pressure.

The reaction can be carried out at room temperature or elevated temperature. Preferably, however, the reaction occurs at a temperature in the range of 80 ° C to 180 ° C. Furthermore, the reaction temperature of 100 ° C to 150 ° C is preferred.

As explained above, the metal compound can be a metal salt. Examples of such salts are nitrates, sulfates, chlorides, fluorides, chlorides, iodides, hydroxides, oxides or alkoxylates. Depending on the metal used, such compounds as hydrates are present. As an example zinc nitrate is mentioned, which is commercially obtainable both in tetra and also as hexahydrate.

The organometallic structural materials according to the present invention contain pores, in particular micro- and / or mesopores. Micropores are defined as those with a diameter of 2 nm or less and mesopores are defined by a diameter in the range of 2 to 50 nm, corresponding in each case according to the definition, as indicated in Pure & Applied Chem. 57 (1985) , 603-619, in particular at page 606 (1976). The presence of micro- and / or mesopores can be examined with the help of sorption measurements, where these measurements determine the absorption capacity of the MOF by nitrogen at 77 kelvin according to DIN 66131 and / or DIN 66134.

Preferably the specific surface area calculated according to the Langmuir model according to DIN 66135 (DIN 66131, 66134) for a MOF in powder form is greater than 5 m²/ g, more preferably about 10 m²/ g, more preferably more than 50 μm²/ g, even more preferably more than 500 μm²/ g, still more preferably greater than 1000 μm²/ g and in particular more than 1500 m²/ g.

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MOF shaped bodies can have a lower specific surface area; however preferably greater than 10 m²/ g, more preferably greater than 50 μm²/ g, even more preferably greater than 500 μm²/ g.

The metal component in the structural material is preferably chosen from groups Ia, IIa, IIIa, IVa to VIIIa and Ib to Vlb. Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, are particularly preferred

Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi. More preferred are Zn, Al, Mg, Ca, Cu, Ni, Fe, Pd, Pt, Ru, Rh, Co, Zr and

You. In particular, Zn, Al, Ni, Cu, Mg, Ca, Fe are preferred. Regarding these ions of these elements, Mg should be mentioned.²⁺, Ca²⁺, Mr²⁺, Ba²⁺, Sc³⁺, Y³⁺, You⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Faith³⁺, Faith²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh⁺, Go²⁺, Go⁺, Neither²⁺, Neither⁺, Ps²⁺, Ps⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al3⁺ Ga³⁺, In³⁺, Tl³⁺, Yes⁴⁺, Yes²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sb⁺, Bi⁵⁺, Bi³⁺ and Bi⁺.

At least one organic compound at least bidentate exhibits at least two atoms, which are in each case chosen independently of one another from the group consisting of oxygen, sulfur and nitrogen, on which the organic compound can bind to the metal in a coordinated manner. These atoms can be part of the structure of the organic compound or be functional groups.

As functional groups on which the mentioned coordinate bonds can be formed, the following functional groups may be mentioned in particular for example: OH, SH, NH2, NH (-RH), N (RH) 2, CH2OH, CH2SH, CH2NH2, CH2NH (-RH), CH2N (-RH) 2, -CO2H, COSH, -CS2H, -NO2, B (OH)₂, -SO3H, -Si (OH) 3, -Ge (OH) 3, -Sn (OH) 3, -Si (SH) 4, -Ge (SH) 4, -Sn (SH) 3, -PO3H2, - AsO3H, AsO4H, -P (SH) 3, -As (SH) 3, -CH (RSH) 2, -C (RSH) 3, -CH (RNH2) 2, -C (RNH2) 3, -CH (ROH ) 2, C (ROH) 3, -CH (RCN) 2, -C (RCN) 3, where R can preferably contain an alkylene group with 1, 2, 3, 4 or 5 carbon atoms such as a methylene group , ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene or n-pentylene, or an aryl group containing 1 or 2 aromatic nuclei such as 2 C rings₆which may optionally be condensed and independently of one another may be suitably substituted with at least one substituent in each case, and / or which may contain independently of each other in each case at least one heteroatom such as for example N, O and / or S. According to preferred modes of operation, functional groups are to be mentioned in which the radical R mentioned above is not present. Correspondingly, among others, -CH (SH) 2, -C (SH) 3, -CH (NH2) 2, CH (NH (RH)) 2, CH (N (RH) 2) 2, C ( NH (RH)) 3, C (N (RH) 2) 3, -C (NH2) 3, -CH (OH) 2, -C (OH) 3, -CH (CN) 2, C (CN) 3 .

The at least two functional groups can in principle be linked in every suitable organic compound as long as it is ensured that the organic compounds exhibiting these functional groups are capable of coordinating bonding and producing the structural material. Preferably the organic compounds, which contain at least the at least two functional groups, are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or both aliphatic and aromatic compounds.

The aliphatic compound or the aliphatic part of the aliphatic as well as aromatic compound can be linear and / or branched and / or cyclic, where several cycles are also possible per compound. More preferably the aliphatic compound or the aliphatic part of both the aliphatic and aromatic compound contains 1 to 18, more preferably 1 to 14, more preferably 1 to 13, more preferably 1 to 12, more preferably 1 to 11 and particularly preferably 1 to 10 carbon atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred here.

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The aromatic compound or the aromatic part of the aromatic as well as aliphatic compound can have one or more nuclei such as, for example, 2, 3, 4 or five nuclei, where the nuclei can be present separately from one another and / or at the same time. least two nuclei be present in condensed form. Particularly preferred is the aromatic compound or the aromatic part of both the aliphatic and aromatic compound exhibiting one, two or three nuclei, where one or two nuclei are particularly preferred. Independently of each other, in addition each nucleus of the mentioned compounds can contain at least one heteroatom such as for example N, O, S, B, P, Si, preferably N, O and / or S. Furthermore, the aromatic compound or the aromatic part of both the aromatic and aliphatic compound preferably contains one or two C nuclei.₆, where the two can be present separately from each other or in a condensed form. In particular benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl are to be mentioned as aromatic compounds.

The at least bidentate organic compound is particularly preferably derived from a di-, tri-, or tetracarboxylic acid or its sulfur analogs. Sulfur analogs are the functional groups -C (= O) SH as well as their tautomers and C (= S) SH, which can be used instead of one or more carboxylic groups.

In the context of the present invention, the term "derivative" means that the at least bidentate organic compound can be present in the structural material in partially deprotonated or totally deprotonated form. In addition, the at least bidentate organic compound may contain other substituents such as -OH, -NH₂, -OCH₃, -CH₃, -NH (CH₃), -N (CH₃)₂, -CN as well as halides.

More preferred is the at least bidentate organic compound of a cyclic or acyclic aliphatic or aromatic hydrocarbon with 1 to 18 carbon atoms which furthermore exhibits as functional groups exclusively at least two carboxy groups.

For example, in the context of the present invention, dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2 -methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'diaminphenylmethane-3,3'- dicarboxylic, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-lsopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octadicarboxylic acid, pentane-3,3-carbonic acid, acid 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic, 4,4'-Diaminodiphenyl-3,3'-dicarboxylic acid, benzidine3,3'-dicarboxylic acid, 1,4-bis- (phenylamino) -benzene-2,5-dicarboxylic acid, 1,1'-naphthyldicarboxylic acid, acid 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinon2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis- (carboxymethyl) piperazine-2,3-dicarboxylic acid, acid 7-chloroquinoline-3,8-dicarboxylic acid, 1- (4-carboxy) -phenyl-3- (4-chloro) -phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7, -hexachloro-5-norborne-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxo-imidazolidine-4,5-dicarboxylic acid, 1 , 4ES 2 349 337 T3 cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoyl-benzene-1,3-dicarbon-ic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid , 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxybenzophenondicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-

2.3- pyrazinedicarboxylic acid, 4,4'-diaminodiphenyletherdiimidodicarboxylic acid, 4,4'-diaminodiphenylmethandiimidodicarboxylic acid, 4,4'-diaminodiphenylsulfondiimidodicarboxylic acid, acid

1,4- naphthaldicarboxylic acid, 2,6-naphthaldicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthaldicarboxylic acid, 2,3-naphthaldicarboxylic acid, 8-methoxy-2,3-naphthaldicarboxylic acid, 8-nitro-2 acid, 3-naphthalene-carbonic, 8-sulfo-2,3-naphthaldicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2 ', 3'-diphenyl-p-terphenyl-4,4-dicarboxylic acid, diphenylether-4,4' acid -dicarboxylic, imidazole-4,5-dicarboxylic acid, 4 (1H) -oxothiochromen-2,8-dicarboxylic acid, 5-tert-butyl- acid

1.3- benzenedicarboxylic acid, 7,8-quinolindicarboxylic acid, 4,5-imidazolecarboxylic acid, 4-cyclohexen-1,2-dicarboxylic acid, hexatriacontane dicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptadicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid , 2,5-dihydroxy-1,4-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonen-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane- 3,3'-dicarboxylic, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin-4 , 11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenon-2 ', 5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole- 3,4-dicarboxylic acid, 1benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoldicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl- 2,3-pyridinedicarboxylic acid or camferdicarboxylic acid, tricarboxylic acids such as 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-, 1,2 acid , 4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo [2,3-F] quinoline-2,7 , 9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid,

1.2.3- propanetricarboxylic acid or aurinetricarboxylic acid, or tetracarboxylic acids such as

1,1-dioxydperyl [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene-1,12-sulfon-3 acid , 4,9,10-tetracarboxylic acid, butane tetracarboxylic acids such as 1,2,3,4-butane tetracarboxylic acid or meso-1,2,3,4-butanttracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, acid 1, 4,7,10,13,16hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexane-tetracarboxylic acid, 1,2,7,8-octane tetracarboxylic acid, 1,4,5,8-naphthane tetracarboxylic acid, 1,2,9,10-decane tetracarboxylic acid, benzophenonetetracarboxylic acid, 3, 3 ', 4,4'-benzo-phenonetetracarboxylic acid, tetrahydrofuranotetracarboxylic acid or cyclopentatetracarboxylic acids such as cyclopentane-1,2,3,4tetracarboxylic.

Very particularly preferably mono-, di-, tri-, tetra- or polynuclear aromatic di-, tri- or tetracarboxylic acids with at least one substituent are used, where appropriate, each of the

ES 2 349 337 T3 nuclei may contain at least one heteroatom, where two or more nuclei may contain the same or different heteroatoms. For example, mononuclear dicarboxylic acids, mononuclear tricarboxylic acids, mononuclear tetracarboxylic acids, dinuclear dicarboxylic acids, dinuclear tricarboxylic acids, dinuclear tetracarboxylic acids, trinuclear dicarboxylic acids, trinuclear tricarboxylic acids, tetranuclear tricarboxylic acids, tetranuclear tricarboxylic acids, tetranuclear tricarboxylic acids, tetranuclear tricarboxylic acids are preferred. or tetranuclear tetracarboxylic acids. Suitable heteroatoms are, for example, N, O, S, B, P, preferred heteroatoms here are N, S and / or O. Correspondingly, suitable substituents include -OH, a nitro group, an amino group. , an alkyl or alkoxy group.

In particular, it is preferred to use as organic compounds at least bidentate acetylene dicarboxylic acid (ADC), campherdicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids, naphthaldicarboxylic acids, biphenyldicarboxylic acids such as, for example, 4,4'-biphenyldicarboxylic acid (BPDC), pyrazinedicarboxylic acids such as 2,5-pyrazinedicarboxylic acid, bipyridinedicarboxylic acids such as 2,2'-bipyridine-dicarboxylic acid, such as 2,2'-bipyridine-5,5'-dicarboxylic acid, benzenetricarboxylic acids such as 1, 2, 3-, 1, 2, 4-benzenetricarboxylic acid or 1, 3, 5-benzenetricarboxylic acid (BTC ), benzene tetracarboxylic acid, adamantatetracarboxylic acid (ATC), adamantandibenzoate (ADB), benzenetribenzoate (BTB), methanetetrabenzoate (MTB), adamantantetrabenzoate or dihydroxyterephthalic acids such as 2,520 dihydroxyterephthalic acid (DHBDC).

Very particularly preferred are, among other things, isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1, 3, 5-benzenetricarboxylic acid, 2,6-naphthaldicarboxylic acid, 1, 4-naphthaldicarboxylic acid, 1, 2, 3, 4- and 1, 2, 4, 5-benzenetetracarboxylic acid, campherdicarboxylic acid or 2,2'-bipyridine-5, 5'-dicarboxylic acid.

Apart from these at least bidentate organic compounds, the organometallic framework material can also comprise one or more monodentate ligands.

The following are examples of organometallic structural materials known in the state of the art. Apart from the characterization of the MOF, the metal as well as the at least bidentate ligand, the solvent is also indicated as well as the parameters of the cells (angle α, β and γ as well as the distances A, B and C in Á). The latter were determined by Rontgen diffraction.

<td>MOF-n</td><td>Molar ratio of components M + L</td><td>Solvent</td><td>α</td><td>β</td><td>γ</td><td>to</td><td>b</td><td>c</td><td>Space group</td>

<td>MOF-0</td><td>Zn (NO3) 2-6H2O H₃(BTC)</td><td>Ethanol</td><td> 90</td><td> 90</td><td> 120</td><td> 16.711</td><td> 16.711</td><td> 14.189</td><td>P6 (3) / Mcm</td>

<td>MOF-2</td><td>Zn (NO3) 2-6H2O (0.246 mmol) H2 (BDC) 0.241 mmol)</td><td>DMF Toluene</td><td> 90</td><td> 102.8</td><td> 90</td><td> 6.718</td><td> 15.49</td><td> 12.43</td><td>P2 (1) / n</td>

<td>MOF-3</td><td>Zn (NO3) 2-6H2O (1.89 mmol) H2 (BDC) (1.93 mmol)</td><td>DMF MeOH</td><td> 99.72</td><td> 111.11</td><td> 108.4</td><td> 9.726</td><td> 9.911</td><td> 10.45</td><td>P-1</td>

<td>MOF-4</td><td>Zn (NO₃)₂-6H₂O (1.00 mmol) H3 (BTC) (0.5 mmol)</td><td>Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 14.728</td><td> 14.728</td><td> 14.728</td><td>P2 (1) 3</td>

<td>MOF-5</td><td>Zn (NO3) 2-6H2O (2.22 mmol) H2 (BDC) (2.17 mmol)</td><td>DMF Chlorobenzene</td><td> 90</td><td> 90</td><td> 90</td><td> 25.669</td><td> 25.669</td><td> 25.669</td><td>Fm-3m</td>

<td>MOF-38</td><td>Zn (NO3) 2-6H2O (0.27 mmol) H3 (BTC) (0.15 mmol)</td><td>DMF Chlorobenzene</td><td> 90</td><td> 90</td><td> 90</td><td> 20.657</td><td> 20.657</td><td> 17.84</td><td>I4cm</td>

<td>MOF-31 Zn (ADC) 2</td><td>Zn (NO₃)₂-6H₂Or 0.4 mmol H₂(ADC) 0.8 mmol</td><td>Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 10.821</td><td> 10.821</td><td> 10.821</td><td>Pn (-3) m</td>

<td>MOF-12 Zn2 (ATC)</td><td>Zn (NO₃)₂-6H₂Or 0.3 mmol Ha (ATC) 0.15 mmol</td><td>Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 15.745</td><td> 16.907</td><td> 18.167</td><td>Pbca</td>

<td>MOF-20 ZnNDC</td><td>Zn (NO3) 2-6H2O 0.37 mmol H2NDC</td><td>DMF</td><td> 90</td><td> 92.13</td><td> 90</td><td> 8.13</td><td> 16.444</td><td> 12.807</td><td>P2 (1) / c</td>

ES 2 349 337 T3

<td></td><td>0.36 mmol</td><td>Chlorobenzene</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>MOF-37</td><td>Zn (NO3) 2-6H2O 0.2 mmol H2NDC 0.2 mmol</td><td>DEF Chlorobenzene</td><td> 72.38</td><td> 83.16</td><td> 84.33</td><td> 9.952</td><td> 11.576</td><td> 15.556</td><td>P-1</td>

<td>MOF-8 Tb2 (ADC)</td><td>Tb (NO3) 3-5H2O 0.10 mmol H2ADC 0.20 mmol</td><td>DMSO MeOH</td><td> 90</td><td> 115.7</td><td> 90</td><td> 19.83</td><td> 9.822</td><td> 19.183</td><td>C2 / c</td>

<td>MOF-9 Tb2 (ADC)</td><td>Tb (NO3) 3-5H2O 0.08 mmol H2 ADB 0.12 mmol</td><td>DMSO</td><td> 90</td><td> 102.09</td><td> 90</td><td> 27.056</td><td> 16.795</td><td> 28.139</td><td>C2 / c</td>

<td>MOF-6</td><td>Tb (NO3) 3-5H2O 0.30 mmol H2 (BDC) 0.30 mmol</td><td>DMF MeOH</td><td> 90</td><td> 91.28</td><td> 90</td><td> 17.599</td><td> 19.996</td><td> 10.545</td><td>P21 / c</td>

<td>MOF-7</td><td>Tb (NO₃)₃-5H₂Or 0.15 mmol H2 (BDC) 0.15 mmol</td><td>H2O</td><td> 102.3</td><td> 91.12</td><td> 101.5</td><td> 6.142</td><td> 10.069</td><td> 10.096</td><td>P-1</td>

<td>MOF-69A</td><td>Zn (NO3) 2-6H2O 0.083 mmol 4.4'BPDC 0.041 mmol</td><td>DEF H2O2 MeNH2</td><td> 90</td><td> 111.6</td><td> 90</td><td> 23.12</td><td> 20.92</td><td> 12</td><td>C2 / c</td>

<td>MOF-69B</td><td>Zn (NO3) 2-6H2O 0.083 mmol 2,6- NCD 0.041 mmol</td><td>DEF H2O2 MeNH2</td><td> 90</td><td> 95.3</td><td> 90</td><td> 20.17</td><td> 18.55</td><td> 12.16</td><td>C2 / c</td>

<td>MOF-11 Cu2 (ATC)</td><td>Cu (NO3) 2-2.5H2O 0.47 mmol H2ATC 0.22 mmol</td><td>H2O</td><td> 90</td><td> 93.86</td><td> 90</td><td> 12.987</td><td> 11.22</td><td> 1.1.336</td><td>C2 / c</td>

<td>MOF-11 Cu2 (ATC) dehydr.</td><td></td><td></td><td> 90</td><td> 90</td><td> 90</td><td> 8.4671</td><td> 8.4671</td><td> 14.44</td><td>P42 / mmc</td>

<td>MOF-14 Cu₃(BTB)</td><td>Cu (NO3) 2-2.5H2O 0.28 mmol H3BTB 0.052 mmol</td><td>H2O DMF EtOH</td><td> 90</td><td> 90</td><td> 90</td><td> 26.946</td><td> 26.946</td><td> 26.946</td><td>Im-3</td>

<td>MOF-32 Cd (ATC)</td><td>Cd (NO3) 2-4H2O 0.24 mmol H4ATC 0.10 mmol</td><td>H2O NaOH</td><td> 90</td><td> 90</td><td> 90</td><td> 13.468</td><td> 13.468</td><td> 13.468</td><td>P (-4) 3m</td>

<td>MOF-n</td><td>Molar ratio of components M + L</td><td>Solvent</td><td>α</td><td>β</td><td>γ</td><td>to</td><td>b</td><td>c</td><td>Space group</td>

<td>MOF-33 Zn2 (ATB)</td><td>ZnCl2 0.15 mmol H4ATB 0.02 mmol</td><td>H2O DMF EtOH</td><td> 90</td><td> 90</td><td> 90</td><td> 19.561</td><td> 15.255</td><td> 23.404</td><td>Imma</td>

<td>MOF-34 Ni (ATC)</td><td>Ni (NO3) 2-6H2O 0.24 mmol H4 ATC 0.10 mmol</td><td>H2O NaOH</td><td> 90</td><td> 90</td><td> 90</td><td> 10.066</td><td> 11.163</td><td> 19.201</td><td>P212121</td>

<td>MOF-36 Zn₂(MTB)</td><td>Zn (NO3) 2-4H2O 0.20 mmol H4 MTB 0.04 mmol</td><td>H2O DMF</td><td> 90</td><td> 90</td><td> 90</td><td> 15.745</td><td> 16.907</td><td> 18.167</td><td>Pbca</td>

<td>MOF-39 Zn3O (HBTB)</td><td>Zn (NO3) 2 4H2O 0.27 mmol H3BTB 0.07 mmol</td><td>H2O DMF EtOH</td><td> 90</td><td> 90</td><td> 90</td><td> 17.158</td><td> 21.591</td><td> 25.308</td><td>Pnma</td>

<td>NO305</td><td>FeCl₂-4H₂O 5.03 mmol formic acid 86.90 mmol</td><td>DMF</td><td> 90</td><td> 90</td><td> 120</td><td> 8.2692</td><td> 8.2692</td><td> 63.566</td><td>R-3c</td>

<td>NO3O6A</td><td>FeCl₂-4H₂O 5.03 mmol formic acid 86.90 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 9.9364</td><td> 18.374</td><td> 18.374</td><td>Pbcn</td>

<td>NO29 similar to MOF-0</td><td>Mn (Ac) 2-4H2O 0.46 mmol H3BTC 0.69 mmol</td><td>DMF</td><td> 120</td><td> 90</td><td> 90</td><td> 14.16</td><td> 33.521</td><td> 33.521</td><td>P-1</td>

<td>BPR48 A2</td><td>Zn (NO3) 2 6H2O 0.012 mmol H2BDC 0.012 mmol</td><td>DMSO Toluene</td><td> 90</td><td> 90</td><td> 90</td><td> 14.5</td><td> 17.04</td><td> 18.02</td><td>Pbca</td>

<td>BPR69 B1</td><td>Cd (NO3) 2 4H2O 0.0212 mmol H2BDC 0.0428 mmol</td><td>DMSO</td><td> 90</td><td> 98.76</td><td> 90</td><td> 14.16</td><td> 15.72</td><td> 17.66</td><td>DC</td>

<td>BPR92 A2</td><td>Co (NO3) 2-6H2O 0.018 mmol H₂BDC 0.018 mmol</td><td>NMP</td><td> 106.3</td><td> 107.63</td><td> 107.2</td><td> 7.5308</td><td> 10.942</td><td> 11.025</td><td>P1</td>

<td>BPR95 C5</td><td>Cd (NO3) 2 4H2O 0.012 mmol H2BDC 0.36 mmol</td><td>NMP</td><td> 90</td><td> 112.8</td><td> 90</td><td> 14.460</td><td> 11.085</td><td> 15.829</td><td>P2 (1) / n</td>

ES 2 349 337 T3

<td>Cu C6H4O6</td><td>Cu (NO3 ^ 2.5H2O 0.370 mmol H2BDC (OH) 2 0.37 mmol</td><td>DMF Chlorobenzene</td><td> 90</td><td> 105.29</td><td> 90</td><td> 15.259</td><td> 14.816</td><td> 14.13</td><td>P2 (1) / c</td>

<td>M (BTC) similar to MOF-0</td><td>Co (SO4) H2O 0.055 mmol H3BTC 0.037 mmol</td><td>DMF</td><td colspan="4">as MOF-0</td><td></td><td></td><td></td>

<td>TXC6H4O6)</td><td>Tlb NOjUIH) 0.370 mmol H2 (C6H4O6) 0.56 mmol</td><td>DMF Chlorobenzene</td><td> 104.6</td><td> 107.9</td><td> 97.147</td><td> 10.491</td><td> 10.981</td><td> 12.541</td><td>P-1</td>

<td>Zn (C2O4)</td><td>ZnCl2 0.370 mmol Oxalic acid 0.37 mmol</td><td>DMF Chlorobenzene</td><td> 90</td><td> 120</td><td> 90</td><td> 9.4168</td><td> 9.4168</td><td> 8.464</td><td>P (-3) 1m</td>

<td>Co (CHO)</td><td>Cone₃)₂^ 5H₂O 0.043 mmol formic acid 1.60 mmol</td><td>DMF</td><td> 90</td><td> 91.32</td><td> 90</td><td> 11.328</td><td> 10.049</td><td> 14.854</td><td>P2 (1) / n</td>

<td>Cd (CHO)</td><td>Cd (NO3Í4H2O 0.185 mmol formic acid 0.185 mmol</td><td>DMF</td><td> 90</td><td> 120</td><td> 90</td><td> 8.5168</td><td> 8.5168</td><td> 22.674</td><td>R-3c</td>

<td>Cu (C3H2O4)</td><td>Cu (NO3h-2.5H₂Or 0.043 mmol malonic acid 0.192 mmol</td><td>DMF</td><td> 90</td><td> 90</td><td> 90</td><td> 8.366</td><td> 8.366</td><td> 11.919</td><td>Q43</td>

<td>Zn6 (NDC) 5 MOF-48</td><td>Zn (NO3h-6H₂O 0.097 mmol 14 NDC 0.069 mmol</td><td>DMF Chlorobenzene H2O2</td><td> 90</td><td> 95.902</td><td> 90</td><td> 19.504</td><td> 16.482</td><td> 14.64</td><td>C2 / m</td>

<td>MOF-47</td><td>Zn (NO3) 2 6H2O 0.185 mmol H2 (BDC [CH3] 4) 0.185 mmol</td><td>DMF Chlorobenzene H2O2</td><td> 90</td><td> 92.55</td><td> 90</td><td> 11.303</td><td> 16.029</td><td> 17.535</td><td>P2 (1) / c</td>

<td>MO25</td><td>Cu (NO3) i-2.5H₂Or 0.084 mmol BPhDC 0.085 mmol</td><td>DMF</td><td> 90</td><td> 112.0</td><td> 90</td><td> 23.880</td><td> 16.834</td><td> 18.389</td><td>P2 (1) / c</td>

<td>MOF-n</td><td>Molar ratio of components M + L</td><td>Solvent</td><td>α</td><td>β</td><td>γ</td><td>to</td><td>b</td><td>c</td><td>Space group</td>

<td>Cu-Tio</td><td>Cu (NO3) i-2.5H₂O 0.084 mmol thiophenedicarboxylic acid 0.085 mmol</td><td>DEF</td><td> 90</td><td> 113.6</td><td> 90</td><td> 15.474 7</td><td> 14.514</td><td> 14.032</td><td>P2 (1) / c</td>

<td>CIBDC1</td><td>Cu (NO3 ^ 2.5H2O 0.084 mmol H2 (BDCCl2) 0.085 mmol</td><td>DMF</td><td> 90</td><td> 105.6</td><td> 90</td><td> 14.911</td><td> 15.622</td><td> 18.413</td><td>C2 / c</td>

<td>MOF-101</td><td>Cu (NO3) i-2.5H₂Or 0.084 mmol BrBDC 0.085 mmol</td><td>DMF</td><td> 90</td><td> 90</td><td> 90</td><td> 21.607</td><td> 20.607</td><td> 20.073</td><td>Fm3m</td>

<td>Zn3 (BTC) 2</td><td>ZnCl₂ 0.033 mmol H3BTC0.033mmol</td><td>DMF EtOH Base added</td><td> 90</td><td> 90</td><td> 90</td><td> 26.572</td><td> 26.572</td><td> 26.572</td><td>Fm-3m</td>

<td>MOF-j</td><td>Co (CH3CO2Í4H2 O (1.65 mmol) H3 (BZC) (0.95 mmol)</td><td>H2O</td><td> 90</td><td> 112.0</td><td> 90</td><td> 17.482</td><td> 12.963</td><td> 6.559</td><td>C2</td>

<td>MOF-n</td><td>Zn (NO3 ^ 6H2O ft (BTC)</td><td>Ethanol</td><td> 90</td><td> 90</td><td> 120</td><td> 16.711</td><td> 16.711</td><td> 14.189</td><td>P6 (3) / lcm</td>

<td>PbBDC</td><td>Pb (NO3) 2 (0.181 mmol) H2 (BDC) (0.181 mmol)</td><td>DMF Ethanol</td><td> 90</td><td> 102.7</td><td> 90</td><td> 8.3639</td><td> 17.991</td><td> 9.9617</td><td>P2 (1) / n</td>

<td>Znhex</td><td>Zn (NO3h-6H₂O (0.171 mmol) H3BTB (0.114 mmol)</td><td>DMF p-xylene Ethanol</td><td> 90</td><td> 90</td><td> 120</td><td> 37.116 5</td><td> 37.117</td><td> 30.019</td><td>P3 (1) c</td>

<td>AS16</td><td>FeBr2 0.927 mmol H2 (BDC) 0.927 mmol</td><td>Anhydrous DMF</td><td> 90</td><td> 90.13</td><td> 90</td><td> 7.2595</td><td> 8.7894</td><td> 19.484</td><td>P2 (1) c</td>

<td>AS27-2</td><td>FeBr2 0.927 mmol H3 (BDC) 0.464 mmol</td><td>Anhydrous DMF</td><td> 90</td><td> 90</td><td> 90</td><td> 26.735</td><td> 26.735</td><td> 26.735</td><td>Fm3m</td>

<td>AS32</td><td>FeCl3</td><td>DMF</td><td> 90</td><td> 90</td><td> 120</td><td> 12.535</td><td> 12.535</td><td> 18.479</td><td>P6 (2) c</td>

<td></td><td>1.23 mmol H2 (BDC) 1.23 mmol</td><td>anhydrous ethanol</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>AS54-3</td><td>FeBr2 0.927 BPDC 0.927 mmol</td><td>DMF, anhydrous n-Propanol</td><td> 90</td><td> 109.98</td><td> 90</td><td> 12.019</td><td> 15.286</td><td> 14.399</td><td>C2</td>

<td>AS61-4</td><td>FeBr₂ 0.927 mmol m-BDC 0.927 mmol</td><td>Anhydrous pyridine</td><td> 90</td><td> 90</td><td> 120</td><td> 13.017</td><td> 13.017</td><td> 14.896</td><td>P6 (2) c</td>

<td>AS68-7</td><td>FeBr₂ 0.927 mmol 7 m-BDC 1.204</td><td>DMF Pyridine</td><td> 90</td><td> 90</td><td> 90</td><td> 18.340</td><td> 10.036</td><td> 18.039</td><td>Pc21</td>

ES 2 349 337 T3

<td></td><td>mmol</td><td>anhydrous</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Zn (ADC)</td><td>Zn (NO3 ^ 6H2O 0.37 mmol H2 (ADC) 0.36 mmol</td><td>DMF Chlorobenzene</td><td> 90</td><td> 99.85</td><td> 90</td><td> 16.764</td><td> 9.349</td><td> 9.635</td><td>C2 / c</td>

<td>MOF-12 Zn2 (ATC)</td><td>Zn (NO₃)₂^ 6H₂Or 0.30 mmol Ha (ATC) 0.15 mmol</td><td>Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 15.745</td><td> 16.907</td><td> 18.167</td><td>Pbca</td>

<td>MOF-20 ZnNDC</td><td>Zn (NO3 ^ 6H2O 0.37 mmol H2NDC 0.36 mmol</td><td>DMF Chlorobenzene</td><td> 90</td><td> 92.13</td><td> 90</td><td> 8.13</td><td> 16.444</td><td> 12.807</td><td>P2 (1) / c</td>

<td>MOF-37</td><td>Zn (NO3 ^ 6H2O 0.20 mmol H2NDC 0.20 mmol</td><td>DEF Chlorobenzene</td><td> 72.38</td><td> 83.16</td><td> 84.33</td><td> 9.952</td><td> 11.576</td><td> 15.556</td><td>P-1</td>

<td>Zn (NDC) (DMSO)</td><td>Zn (NO3 ^ 6H2O H2NDC</td><td>DMSO</td><td> 68.08</td><td> 75.33</td><td> 88.31</td><td> 8.631</td><td> 10.207</td><td> 13.114</td><td>P-1</td>

<td>Zn (NDC)</td><td>Zn (NO3 ^ 6H2O H2NDC</td><td></td><td> 90</td><td> 99.2</td><td> 90</td><td> 19.289</td><td> 17.628</td><td> 15.052</td><td>C2 / c</td>

<td>Zn (HPDC)</td><td>Zn (NO₃)₂4_H2O 0.23 mmol H2 (HPDC) 0.05 mmol</td><td>DMF H2O</td><td> 107.9</td><td> 105.06</td><td> 94.4</td><td> 8.326</td><td> 12.085</td><td> 13.767</td><td>P-1</td>

<td>Co (HPDC)</td><td>Co (NO3 ^ 6H2O 0.21 mmol H2 (HPDC) 0.06 mmol</td><td>DMF H2O / Ethanol</td><td> 90</td><td> 97.69</td><td> 90</td><td> 29.677</td><td> 9.63</td><td> 7.981</td><td>C2 / c</td>

<td>Zn3 (PDC) 2.5</td><td>Zn (NOih-4H₂Or 0.17 mmol H2 (HPDC) 0.05 mmol</td><td>DMF / CIBz. H2O / TEA</td><td> 79.34</td><td> 80.8</td><td> 85.83</td><td> 8.564</td><td> 14.046</td><td> 26.428</td><td>P-1</td>

<td>Cd2</td><td>Cd (NO3f4H2O</td><td>Goal-</td><td> 70.59</td><td> 72.75</td><td> 87.14</td><td> 10.102</td><td> 14.412</td><td> 14.964</td><td>P-1</td>

<td>MOF-n</td><td>Molar ratio of components M + L</td><td>Solvent</td><td>α</td><td>β</td><td>γ</td><td>to</td><td>b</td><td>c</td><td>Space group</td>

<td>(TPDC) 2</td><td>0.06 mmol H2 (HPDC) 0.06 mmol</td><td>nol / CHP H2O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Tb (PDC) 1.5</td><td>Tb (NO3V5H2O 0.21 mmol H2 (PDC) 0.034 mmol</td><td>DMF H2O / Ethanol</td><td> 109.8</td><td> 103.61</td><td> 100.14</td><td> 9.829</td><td> 12.11</td><td> 14.628</td><td>P-1</td>

<td colspan="10"></td>

<td>ZnDBP</td><td>Zn (NO₃)₂^ 6H₂Or 0.05 mmol dibenzylphosphate 0.10 mmol</td><td>MeOH</td><td> 90</td><td> 93.67</td><td> 90</td><td> 9.254</td><td> 10.762</td><td> 27.93</td><td>P2 / n</td>

<td>Zn3 (BPDC)</td><td>ZnBr2 0.021 mmol 4.4'BPDC 0.005 mmol</td><td>DMF</td><td> 90</td><td> 102.76</td><td> 90</td><td> 11.49</td><td> 14.79</td><td> 19.18</td><td>P21 / n</td>

<td>CdBDC</td><td>Cd (NO3f4H2O 0.100 mmol H2 (BDC) 0.401 mmol</td><td>DMF Na2SiO3 (ac.)</td><td> 90</td><td> 95.85</td><td> 90</td><td> 11.2</td><td> 11.11</td><td> 16.71</td><td>P21 / n</td>

<td>Cd-mBDC</td><td>Cd (NO3) 2 ^ 4H2O 0.009 mmol H2 (mBDC) 0.018 mmol</td><td>DMF MeNH2</td><td> 90</td><td> 101.1</td><td> 90</td><td> 13.69</td><td> 18.25</td><td> 14.91</td><td>C2 / c</td>

<td>Zn4OBND C</td><td>Zn (NO3 ^ 6H2O 0.041mmol BNDC</td><td>DEF MeNH2 H2O2</td><td> 90</td><td> 90</td><td> 90</td><td> 22.35</td><td> 26.05</td><td> 59.56</td><td>Fmmm</td>

<td>Eu (TCA)</td><td>EPNO3V6H2O 0.14 mmol TCA 0.026 mmol</td><td>DMF Chlorobenzene</td><td> 90</td><td> 90</td><td> 90</td><td> 23.325</td><td> 23.325</td><td> 23.325</td><td>Pm-3n</td>

<td>Tb (TCA)</td><td>Tb (NO3V6H2O 0.069 mmol TCA 0.026 mmol</td><td>DMF Chlorobenzene</td><td> 90</td><td> 90</td><td> 90</td><td> 23.272</td><td> 23.272</td><td> 23.272</td><td>Pm-3n</td>

<td>Formate</td><td>Ce (NO3MH2O 0.138 mmol Formic acid 0.43 mmol</td><td>H2O</td><td>90 Ethanol</td><td> 90</td><td> 120</td><td> 10.668</td><td> 10.667</td><td> 4.107</td><td>R-3m</td>

<td></td><td>FeCl₂4H₂O 5.03 mmol Formic acid 86.90 mmol</td><td>DMF</td><td> 90</td><td> 90</td><td> 120</td><td> 8.2692</td><td> 8.2692</td><td> 63.566</td><td>R-3c</td>

<td></td><td>FeCl₂4H₂O 5.03 mmol Formic acid 86.90 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 9.9364</td><td> 18.374</td><td> 18.374</td><td>Pbcn</td>

<td></td><td>FeCl₂4H₂O 5.03 mmol Formic acid 86.90 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 8.335</td><td> 8.335</td><td> 13.34</td><td>P-31c</td>

<td>NO330</td><td>FeCl₂4H₂Or 0.50 mmol Formic acid. 8.69 mmol</td><td>Formamide</td><td> 90</td><td> 90</td><td> 90</td><td> 8.7749</td><td> 11.655</td><td> 8.3297</td><td>Pnna</td>

ES 2 349 337 T3

<td>NO332</td><td>FeCl₂4H₂O 0.50 mmol Formic acid 8.69 mmol</td><td>DIP</td><td> 90</td><td> 90</td><td> 90</td><td> 10.031 3</td><td> 18.808</td><td> 18.355</td><td>Pbcn</td>

<td>NO333</td><td>FeCl₂4H₂O 0.50 mmol Formic acid 8.69 mmol</td><td>DBF</td><td> 90</td><td> 90</td><td> 90</td><td> 45.275 4</td><td> 23.861</td><td> 12.441</td><td>Cmcm</td>

<td>NO335</td><td>FeCl₂4H₂O 0.50 mmol Formic acid 8.69 mmol</td><td>CHF</td><td> 90</td><td> 91.372</td><td> 90</td><td> 11.596 4</td><td> 10.187</td><td> 14.945</td><td>P21 / n</td>

<td>NO336</td><td>FeCl₂4H₂O 0.50 mmol Formic acid 8.69 mmol</td><td>MFA</td><td> 90</td><td> 90</td><td> 90</td><td> 11.794 5</td><td> 48.843</td><td> 8.4136</td><td>Pbcm</td>

<td>NO13</td><td>Mn (Ac)₂4H₂O 0.46 mmol benzoic acid 0.92 mmol bipyridine 0.46 mmol</td><td>Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 18.66</td><td> 11.762</td><td> 9.418</td><td>Pbcn</td>

<td>NO29 similar to MOF-0</td><td>Mn (Ac) 2 ^ 4H2O 0.46 mmol H3BTC 0.69 mmol</td><td>DMF</td><td> 120</td><td> 90</td><td> 90</td><td> 14.16</td><td> 33.521</td><td> 33.521</td><td>P-1</td>

<td>Mn (hfac)₂(O2CC6H₅)</td><td>Mn (Ac)₂4H₂Or 0.46 mmol Hfac 0.92 mmol bipyridine 0.46 mmol</td><td>Ether</td><td> 90</td><td> 95.32</td><td> 90</td><td> 9.572</td><td> 17.162</td><td> 14.041</td><td>C2 / c</td>

<td>BPR43G2</td><td>Zn (NO3 ^ 6H2O 0.0288 mmol H2BDC 0.0072 mmol</td><td>DMF CH₃CN</td><td> 90</td><td> 91.37</td><td> 90</td><td> 17.96</td><td> 6.38</td><td> 7.19</td><td>C2 / c</td>

<td>BPR48A2</td><td>Zn (NO3) 2 6H2O 0.012 mmol H2BDC 0.012 mmol</td><td>DMSO Toluene</td><td> 90</td><td> 90</td><td> 90</td><td> 14.5</td><td> 17.04</td><td> 18.02</td><td>Pbca</td>

<td>MOF-n</td><td>Molar ratio of components M + L</td><td>Solvent</td><td>α</td><td>β</td><td>γ</td><td>to</td><td>b</td><td>c</td><td>Space group</td>

<td>BPR49B1</td><td>Zn (NO3) 2 6H2O 0.024 mmol H2BDC 0.048 mmol</td><td>DMSO Methanol</td><td> 90</td><td> 91.172</td><td> 90</td><td> 33.181</td><td> 9.824</td><td> 17.884</td><td>C2 / c</td>

<td>BPR56E1</td><td>Zn (NO3) 2 6H2O 0.012 mmol H2BDC 0.024 mmol</td><td>DMSO n- Propanol</td><td> 90</td><td> 90.096</td><td> 90</td><td> 14.587 3</td><td> 14.153</td><td> 17.183</td><td>P2 (1) / n</td>

<td>BPR68D10</td><td>Zn (NO3) 2 6H2O 0.0016 mmol H3BTC 0.0064 mmol</td><td>DMSO Benzene</td><td> 90</td><td> 95.316</td><td> 90</td><td> 10.062 7</td><td> 10.17</td><td> 16.413</td><td>P2 (1) / c</td>

<td>BPR69B1</td><td>Cd (NO3) 2 4H2O</td><td>DMSO</td><td> 90</td><td> 98.76</td><td> 90</td><td> 14.16</td><td> 15.72</td><td> 17.66</td><td>DC</td>

<td></td><td>0.0212 mmol H₂BDC 0.0428 mmol</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>BPR73E4</td><td>Cd (NO3) 2 4H2O 0.006 mmol H2BDC 0.003 mmol</td><td>DMSO Toluene</td><td> 90</td><td> 92.324</td><td> 90</td><td> 8.7231</td><td> 7.0568</td><td> 18.438</td><td>P2 (1) / n</td>

<td>BPR76D5</td><td>Zn (NO3) 2 6H2O 0.0009 mmol H2BZPDC 0.0036 mmol</td><td>DMSO</td><td> 90</td><td> 104.17</td><td> 90</td><td> 14.419 1</td><td> 6.2599</td><td> 7.0611</td><td>Pc</td>

<td>BPR80B5</td><td>Cd (NO3Í4H2O 0.018 mmol H2BDC 0.036 mmol</td><td>DMF</td><td> 90</td><td> 115.11</td><td> 90</td><td> 28.049</td><td> 9.184</td><td> 17.837</td><td>C2 / c</td>

<td>BPR80H5</td><td>Cd (NO3) 2 4H2O 0.027 mmol H2BDC 0.027 mmol</td><td>DMF</td><td> 90</td><td> 119.06</td><td> 90</td><td> 11.474 6</td><td> 6.2151</td><td> 17.268</td><td>P2 / c</td>

<td>BPR82C6</td><td>Cd (NO3) 2 4H2O 0.0068 mmol H2BDC 0.202 mmol</td><td>DMF</td><td> 90</td><td> 90</td><td> 90</td><td> 9.7721</td><td> 21.142</td><td> 27.77</td><td>Fdd2</td>

<td>BPR86C3</td><td>Co (NO3) 2 6H2O 0.0025 mmol H2BDC 0.075 mmol</td><td>DMF</td><td> 90</td><td> 90</td><td> 90</td><td> 18.344 9</td><td> 10.031</td><td> 17.983</td><td>Pca2 (1)</td>

<td>BPR86H6</td><td>CdCNO ^ -oHjO 0.010 mmol H2BDC 0.010 mmol</td><td>DMF</td><td> 80.98</td><td> 89.69</td><td> 83.412</td><td> 9.8752</td><td> 10.263</td><td> 15.362</td><td>P-1</td>

<td></td><td>Co (NO3) 2 6H2O</td><td>NMP</td><td> 106.3</td><td> 107.63</td><td> 107.2</td><td> 7.5308</td><td> 10.942</td><td> 11.025</td><td>P1</td>

<td>BPR95A2</td><td>Zn (NO3) 2 6H2O 0.012 mmol H2BDC 0.012 mmol</td><td>NMP</td><td> 90</td><td> 102.9</td><td> 90</td><td> 7.4502</td><td> 13.767</td><td> 12.713</td><td>P2 (1) / c</td>

<td>CUC6F4O4</td><td>Cu (NO3ÍJ.5H2O 0.370 mmol H2BDC (OH) 2 0.37 mmol</td><td>DMF Chlorobenzene</td><td> 90</td><td> 98.834</td><td> 90</td><td> 10.967 5</td><td> 24.43</td><td> 22.553</td><td>P2 (1) / n</td>

<td>Formic Faith</td><td>FeCl₂4H₂O 0.370 mmol Formic acid 0.37 mmol</td><td>DMF</td><td> 90</td><td> 91.543</td><td> 90</td><td> 11.495</td><td> 9.963</td><td> 14.48</td><td>P2 (1) / n</td>

<td>Formic Mg</td><td>MgCNO ^ -óHjO 0.370 mmol Formic acid 0.37 mmol</td><td>DMF</td><td> 90</td><td> 91.359</td><td> 90</td><td> 11.383</td><td> 9.932</td><td> 14.656</td><td>P2 (1) / n</td>

<td>MgC6H4O6</td><td>Mg (NO3 ^ 6H2O</td><td>DMF</td><td> 90</td><td> 96.624</td><td> 90</td><td> 17.245</td><td> 9.943</td><td> 9.273</td><td>C2 / c</td>

ES 2 349 337 T3

<td></td><td>0.370 mmol H2BDC (OH) 2 0.37 mmol</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Zn C2H4BDC MOF-38</td><td>ZnCl2 0.44 mmol CBBDC 0.261 mmol</td><td>DMF</td><td> 90</td><td> 94.714</td><td> 90</td><td> 7.3386</td><td> 16.834</td><td> 12.52</td><td>P2 (1) / n</td>

<td>MOF-49</td><td>ZnCl2 0.44 mmol m-BDC 0.261 mmol</td><td>DMF CH3CN</td><td> 90</td><td> 93.459</td><td> 90</td><td> 13.509</td><td> 11.984</td><td> 27.039</td><td>P2 / c</td>

<td>MOF-26</td><td>Cu (NO3) 2-5H2O 0.084 mmol DCPE 0.085 mmol</td><td>DMF</td><td> 90</td><td> 95.607</td><td> 90</td><td> 20.879 7</td><td> 16.017</td><td> 26.176</td><td>P2 (1) / n</td>

<td>MOF-112</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol o- Br-m-BDC 0.085 mmol</td><td>DMF Ethanol</td><td> 90</td><td> 107.49</td><td> 90</td><td> 29.324 1</td><td> 21.297</td><td> 18.069</td><td>C2 / c</td>

<td>MOF-109</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol KDB 0.085 mmol</td><td>DMF</td><td> 90</td><td> 111.98</td><td> 90</td><td> 23.880 1</td><td> 16.834</td><td> 18.389</td><td>P2 (1) / c</td>

<td>MOF-111</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol o- BrBDC 0.085 mmol</td><td>DMF Ethanol</td><td> 90</td><td> 102.16</td><td> 90</td><td> 10.676 7</td><td> 18.781</td><td> 21.052</td><td>C2 / c</td>

<td>MOF-110</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol Thiophenedicarboxylic acid 0.085 mmol</td><td>DMF</td><td> 90</td><td> 90</td><td> 120</td><td> 20.065 2</td><td> 20.065</td><td> 20.747</td><td>R-3 / m</td>

<td>MOF-n</td><td>Molar ratio of components M + L</td><td>Solvent</td><td>α</td><td>β</td><td>γ</td><td>to</td><td>b</td><td>c</td><td>Space group</td>

<td>MOF-107</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol Thiophenedicarboxylic acid 0.085 mmol</td><td>DEF</td><td> 104.8</td><td> 97.075</td><td> 95.20 6</td><td> 11.032</td><td> 18.067</td><td> 18.452</td><td>P-1</td>

<td>MOF-108</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol Thiophenedicarboxylic acid 0.085 mmol</td><td>DBF / Methanol</td><td> 90</td><td> 113.63</td><td> 90</td><td> 15.474 7</td><td> 14.514</td><td> 14.032</td><td>C2 / c</td>

<td>MOF-102</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol H2 (BDCCl2) 0.085 mmol</td><td>DMF</td><td> 91.63</td><td> 106.24</td><td> 112.01</td><td> 9.3845</td><td> 10.794</td><td> 10.831</td><td>P-1</td>

<td>Clbdc1</td><td>Cu (NO3) 2-2.5H2O 0.084 mmol H2 (BDCCl2) 0.085 mmol</td><td>DEF</td><td> 90</td><td> 105.56</td><td> 90</td><td> 14.911</td><td> 15.622</td><td> 18.413</td><td>P-1</td>

<td>Cu (NMOP)</td><td>Cu (NO3) 2-2.5H2O</td><td>DMF</td><td> 90</td><td> 102.37</td><td> 90</td><td> 14.923</td><td> 18.727</td><td> 15.529</td><td>P2 (1) / m</td>

<td></td><td>0.084 mmol NBDC 0.085 mmol</td><td></td><td></td><td></td><td></td><td> 8</td><td></td><td></td><td></td>

<td>Tb (BTC)</td><td>Tb (NO3) 3-5H2O 0.033 mmol H3BTC 0.033 mmol</td><td>DMF</td><td> 90</td><td> 106.02</td><td> 90</td><td> 18.698 6</td><td> 11.368</td><td> 19.721</td><td></td>

<td>Zn3 (BTC) 2 Honk</td><td>ZnCl2 0.033 mmol H3BTC 0.033 mmol</td><td>DMF Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 26.572</td><td> 26.572</td><td> 26.572</td><td>Fm-3m</td>

<td>Zn4O (NDC)</td><td>Zn (NO3) 2-4H2O 0.066 mmol 14NDC 0.066 mmol</td><td>DMF Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 41.559 4</td><td> 18.818</td><td> 17.574</td><td>aba2</td>

<td>CdTDC</td><td>Cd (NO3) 2-4H2O 0.014 mmol Thiophene 0.040 mmol DABCO 0.020 mmol</td><td>DMF H2O</td><td> 90</td><td> 90</td><td> 90</td><td> 12.173</td><td> 10.485</td><td> 7.33</td><td>Pmma</td>

<td>IRMOF-2</td><td>Zn (NO₃)₂-4H₂O 0.160 mmol o-Br- BDC 0.60 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 25.772</td><td> 25.772</td><td> 25.772</td><td>Fm-3m</td>

<td>IRMOF-3</td><td>Zn (NO3) 2-4H2O 0.20 mmol H2N- BDC 0.60 mmol</td><td>DEF Ethanol</td><td> 90</td><td> 90</td><td> 90</td><td> 25.747</td><td> 25.747</td><td> 25.747</td><td>Fm-3m</td>

<td>IRMOF-4</td><td>Zn (NO3) 2-4H2O 0.11 mmol [C3H7O] 2-BDC 0.48 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 25.849</td><td> 25.849</td><td> 25.849</td><td>Fm-3m</td>

<td>IRMOF-5</td><td>Zn (NO3) 2-4H2O 0.13 mmol [C5H11O] 2-BDC 0.50 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 12.882</td><td> 12.882</td><td> 12.882</td><td>Pm-3m</td>

<td>IRMOF-6</td><td>Zn (NO3) 2-4H2O 0.20 mmol [C2H4] -BDC 0.60 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 25.842</td><td> 25.842</td><td> 25.842</td><td>Fm-3m</td>

<td>IRMOF-7</td><td>Zn (NO₃)₂-4H₂Or 0.07 mmol 1.4NDC 0.20 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 12.914</td><td> 12.914</td><td> 12.914</td><td>Pm-3m</td>

<td>IRMOF-8</td><td>Zn (NO₃)₂-4H₂Or 0.55 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 30.092</td><td> 30.092</td><td> 30.092</td><td>Fm-3m</td>

ES 2 349 337 T3

<td></td><td>2.6NDC 0.42 mmol</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>IRMOF-9</td><td>Zn (NO₃) 2-4H2O 0.05 mmol BPDC 0.42 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 17.147</td><td> 23.322</td><td> 25.255</td><td>Pnnm</td>

<td>IRMOF-10</td><td>Zn (NO₃) 2-4H2O 0.02 mmol BPDC 0.012 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 34.281</td><td> 34.281</td><td> 34.281</td><td>Fm-3m</td>

<td>IRMOF-11</td><td>Zn (NO₃) 2-4H2Ü 0.05 mmol HPDC 0.20 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 24.822</td><td> 24.822</td><td> 24.822</td><td>R-3m</td>

<td>IRMOF-12</td><td>Zn (NO₃) 2-4H2Ü 0.017 mmol HPDC 0.12 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 34.281</td><td> 34.281</td><td> 34.281</td><td>Fm-3m</td>

<td>IRMOF-13</td><td>Zn (NO₃) 2-4H2Ü 0.048 mmol PDC 0.31 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 24.822</td><td> 24.822</td><td> 56.734</td><td>R-3m</td>

<td>IRMOF-14</td><td>Zn (NO₃) 2-4H2Ü 0.17 mmol PDC 0.12 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 34.381</td><td> 34.381</td><td> 34.381</td><td>Fm-3m</td>

<td>IRMOF-15</td><td>Zn (NO₃) 2-4H2Ü 0.063 mmol TPDC 0.025 mmol</td><td>DEF</td><td> 90</td><td> 90</td><td> 90</td><td> 21.459</td><td> 21.459</td><td> 21.459</td><td>Im-3m</td>

<td>MOF-n</td><td>Molar ratio of components M + L</td><td>Solvent</td><td>α</td><td>β</td><td>γ</td><td>to</td><td>b</td><td>c</td><td>Space group</td>

<td>IRMOF-16</td><td>Zn (NO3) 2-4H2Ü 0.0126 mmol TPDC 0.05 mmol</td><td>DEF NMP</td><td> 90</td><td> 90</td><td> 90</td><td> 21.49</td><td> 21.49</td><td> 21.49</td><td>Pm-3m</td>

ADC Acetylene dicarboxylic acid

NDC Naphthaldicarboxylic acid

BDC Benzenedicarboxylic acid

ATC Adamantane tetracarboxylic acid

BTC Benzenetricarboxylic acid

BTB Benzenetribenzoic acid

MTB Methane tetrabenzoic acid

ATB Adamantane tetrabenzoic acid

ADB Adamantandibenzoic acid

Other MOFs are MOF-177, MOF-178, MOF-74, MOF-235, MOF-236, MOF-69 to 80, MOF-501, MOF-502, which are described in the literature.

Within the framework of the present invention, so-called IRMOF materials, in particular IRMOF-1 (= MOF-5), are very particularly preferred.

In the case of organic boron structural materials, an organic compound appears in place of the metal ion that exhibits at least two boron groups. Also, here the structure of the compound can be used, as explained above for the organometallic structural material, organic compound at least bidentate. Furthermore, however these have to exhibit at least two groups (-B (OH) 2). Examples are benzene-boric acids, in particular benzene-1,2-diboric acid. Each of the boron groups reacts with at least one at least bifunctional organic compound, which in principle can be used as the least bidentate organic compound for the organometallic structural material. The same structures as well as the above-mentioned functional groups can be used here. However, additionally they can also be organic boron-containing compounds, which can be the same or different from the first compound exhibiting at least two boron groups. Preferably the at least bifunctional organic compound are aromatic di or polyols or di- or polyboric acids. Thus, the COF materials are compounds from a first organic compound that exhibits at least two boron groups as well as a second organic compound with at least two

ES 2 349 337 T3 functional groups. In addition, other compounds that are not necessarily bi- or multifunctional can be used.

The non-aqueous organic solvent is preferably a C1-6 alkanol, dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc), acetonitrile, toluene, dioxane, benzene , chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), ethyl acetate, also halogenated C1-200 alkane, sulfolane, glycol, N-methylpyrrolidone (NMP), gamma-butyrolactone, alicyclic alcohols as well as cyclohexanol, ketones, such as acetone or acetylacetone, cycloketones, such as cyclohexanone, sulfolene, or mixtures of them.

A C1-6 alkanol describes an alcohol with 1 to 6 carbon atoms. Examples here are methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, pentanol, hexanol as well as mixtures thereof.

A likewise halogenated C1-200 alkane exhibits an alkane with 1 to 200 carbon atoms, where one or more or even all of the hydrogen atoms can or can be replaced by halogen, preferably chlorine or fluorine, in particular chlorine. Examples here are chloroform, dichloromethane, tetrachloromethane, dichloroethane, hexane, heptane, octane as well as mixtures thereof.

DMF, DEF, DMAc and NMP are preferred solvents. DMF is particularly preferred.

The non-aqueous concept preferably relates to a solvent that does not exceed a maximum water content of 10% by weight, more preferred 5% by weight, even more preferred 1% by weight, still preferred 0.1% by weight, particularly preferred 0.01% by weight based on total weight of the solvent. Preferably the maximum total water content of the liquid phase of the reaction mixture before transformation is 10% by weight, more preferably 5% by weight and even more preferably 1% by weight. Furthermore at the end of the transformation the total maximum content of water is at most 3% by weight, more preferably at most 1% by weight and usually preferably at most 0.5% by weight.

The determination of the water content can be carried out by the usual methods for the experts. Preferably the water content is determined according to the Karl Fischer method (for example Rompp Chemie Lexikon vol. 3 (1995), p. 2161, publisher Georg Thieme).

The term solvent refers to pure solvents as well as mixtures of different solvents.

After the reaction, several finishing steps can occur, which are preferably carried out under the exclusion of moisture. They can be filtering, drying, washing, drying, extraction, calcination or shaping steps.

A calcination step is particularly preferred. Typically, the temperature set here is greater than 250 ° C, preferably 300 ° C to 400 ° C.

As a result of the calcination step, starting compounds can be released, which eventually remain in the pores.

Complementary or alternative to this, the removal of the starting materials from the pores of the porous organic structural material may occur, by treating the formed structural material with a non-aqueous solvent. Here, in one type of extraction method, the starting material to be removed is leached and, if necessary, replaced in the structural material by a solvent molecule. This delicate method is particularly suitable when the starting materials are high-boiling compounds. Treatment occurs for at least 30 minutes and can typically be run for up to two days. This can take place at room temperature or elevated temperature. Preferably this occurs at elevated temperature, preferably at least 40 ° C, preferably 60 ° C. Furthermore, boiling point extraction of the solvent used (under reflux) is preferred.

ES 2 349 337 T3

Treatment can occur in a single container by suspending and agitating the structural material. Extraction equipment such as Soxhlet equipment can also be used, in particular technical extraction equipment.

Suitable solvents are those mentioned above, such as, for example, C1-6 alkanol, dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), acetonitrile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, tetrahydrofuran (THF), ethyl acetate, optionally halogenated C1-200 alkane, sulfolane, glycol, N-methylpyrrolidone (NMP), gamma-butyrolactone, alicyclic alcohols such as cyclohexanol, ketones, such as acetone or acetylacetone, cycloketones, such as cyclohexanone or mixtures thereof.

Methanol, ethanol, propanol, acetone, MEK, and mixtures thereof are preferred.

A very particularly preferred extraction agent is methanol.

The solvent used for the extraction may be the same or different from that of the reaction of the at least one metal compound with the at least one organic compound that is at least bidentate. In particular, in the extraction it is not absolutely necessary although it is preferred that the solvent is anhydrous.

The organic structural material can be present in the form of a powder or as an agglomerate. The structural material can be used as such or it can be transformed into a molded body. Preferred methods for the production of shaped articles are granulation or tableting here. In the production of molded articles, the structural material can have other materials, such as binders, release agents and other additives, which can be added during production. It is also conceivable that the structural material exhibits other components, such as absorbents such as activated carbon or the like.

With regard to the possible geometries of the shaped bodies, there are essentially no limitations. For example, among other pellets, such as disc-shaped pellets, specks, spheres, granules, extrudates, such as ropes, honeycombs, gratings or hollow bodies, are to be mentioned.

Fundamentally all suitable methods are possible for the production of these hollow bodies. The following variants of the method are particularly preferred:

- kneading / grinding the structural material alone or together with at least one binder and / or at least one pasting material and / or at least one guide compound to obtain a mixture; shaping of the mixture obtained by means of at least one suitable method such as extrusion; optionally washing and / or drying and / or calcining the extrudate; optionally finished.

- Tableted together with at least one binder and / or other auxiliary substances.

- Application of the structural material on at least one support material, if necessary porous. The material obtained can then be reconditioned to a molded body according to the method described above.

- application of the structural material on at least one substrate, if necessary porous.

Kneading / grinding and shaping can occur according to any suitable method, as described for example in Ullmanns Enzyklopadie der Technischen Chemie, 4^to. edition, volume 2, pp. 313 and following (1972).

For example kneading / grinding and shaping can occur by means of a piston press, roller press in the presence or absence of at least one binder material, compounding, pelleting, tableting, extrusion, co-extrusion, foaming, spinning, coated , granulated,

ES 2 349 337 T3 preferably spray granulate, spray, spray dried or a combination of two or more of these methods.

Pellets and / or tablets are very particularly preferably produced.

Kneading and / or shaping can occur at elevated temperatures such as for example in the ambient temperature range to 300 ° C and / or elevated pressure such as for example in the normal pressure range up to a few hundred bar and / or in an atmosphere of protective gas such as in the presence of a noble gas, nitrogen or a mixture of two or more of them.

According to another embodiment, the kneading and / or shaping is carried out by adding at least one binder, where basically any chemical compound is used as a binder that guarantees the desired viscosity of the mass to be used in the kneading and / or shaping. be kneaded and / or shaped. Furthermore, in the sense of the present invention the binders can be both viscosity-increasing and viscosity-reducing compounds.

As other preferred binders, mention may be made, for example, of aluminum oxide or binders containing aluminum oxide, as described for example in WO 94/29408, silicon dioxide as described for example in EP 0 592 050 A1, mixtures of silicon dioxide and aluminum oxide as described for example in WO 94/13584, clay minerals as described for example in JP 03-037156 A, for example montmorillonite, kaolin, bentonite, halloisite, dickite, nacrita and anauxite, alkoxysilanes as described for example in EP 0 102 544 B1, for example tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or for example trialkoxysilanes such as for example trimethoxysilane, triethoxysilane, triproxythoxysilane, tributoxysilane, triproxythoxysilane example tetraalkoxytitanates such as tetramethoxytitanate, tetraethoxytitanate, tetrapropoxytitanate, tetrabutoxytitanate, or for example trialkoxycytitanates such as for example trimethoxytitanate, triethoxytitanate, tripropoxytitanate, tributoxytitanate, alkoxyzirconates, for example tetraalkoxycyrconates such as for example tetramethoxycyrconate, tetraethoxyirconate, tetrapropoxycyrconate, tetrabutoxycyrconate, for example tributoxytitanate, alkoxycyrconates, for example tetraalkoxycyrconates such as for example tetramethoxycyrconate, tetraethoxyirconate, tetrapropoxycyrconate, tetrabutoxycyrcoxytoxymate, for example tributoxyrcoxytoxymate, triphoxychonate, for example tributoxyrcoxytoxytoles and / or graphite.

As viscosity-increasing compounds, it is also possible to use, for example, optionally in addition to the compounds mentioned above, an organic compound and / or a hydrophilic polymer, such as cellulose or a cellulose derivative, such as methylcellulose and / or a polyacrylate / or a polymethacrylate and / or a polyvinyl alcohol and / or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran and / or a polyethylene oxide.

As pasting agent, preferably water or at least one alcohol such as, for example, a monoalcohol with 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, can be used. , 2-methyl-1-propanol or 2-methyl-2-propanol or a mixture of water and at least one of the alcohols mentioned or a polyhydric alcohol such as a glycol, preferably a polyhydric alcohol miscible in water, alone or as a mixture with water and / or at least one of the mentioned monohydric alcohols.

Other additives that can be used for kneading and / or shaping are, among other things, amines or derivatives of amines, such as tetraalkylammonium compounds or amino alcohols and carbonate-containing compounds such as calcium carbonate. These other additives are described in EP 0 389 041 A1, EP 0 200 260 A1 or WO 95/19222.

Basically, the order of the additives such as guide compound, binder, pasting agent, substance that increases viscosity in shaping and kneading, is not critical.

ES 2 349 337 T3

According to another preferred way of operating, the molded body obtained by kneading and / or shaping is subjected to at least one drying, which is generally carried out at a temperature in the range of 25 to 500 ° C, preferably in the range from 50 to 500 ° C and particularly preferred in the range from 100 to 350 ° C. It is also possible to dry under vacuum or under a protective gas atmosphere or by spray drying.

According to a particularly preferred way of operating within the framework of this drying process, at least one of the compounds added as additives is removed from the shaped body at least partially.

Examples

Comparison example 1: conventional synthesis of MOF-5

96.7 g of Zn (NO₃)₂* 4H₂O and 20.8 g of terephthalic acid in 2825 g of DEF (water content of 0.02% according to K. Fischer). The reaction mixture (total water content of 1% according to K. Fischer) is kept for 3.5 h at 130 ° C. At the end of the reaction time, the water content of the reaction solution is 1.1%. After cooling, the dry matter is filtered off and washed 4 x 500 ml with anhydrous acetone. First of all, the solid substance is pre-dried at room temperature in a stream of nitrogen for 2 to 4 days and then it is evacuated in a vacuum drying cabinet for 16 h (&lt;1 mbar).

Before the determination of the surface with N2, the samples are evacuated in each case for more hours at 200 ° C.

The following surface values ​​were determined (according to Langmuir):

<td>Sample</td><td>Surface [m / g]</td>

<td>A (MH 148)</td><td> 2674</td>

<td>B (MH 150)</td><td> 3016</td>

<td>C (MH 155)</td><td> 2904</td>

<td>D (MH 158)</td><td> 3530</td>

<td>E (MH 159)</td><td> 2279</td>

<td>F (MH 160)</td><td> 3684</td>

<td>G (MH 161)</td><td> 2038</td>

<td>H (MH 164)</td><td> 2811</td>

<td colspan="2">Average 2867 ± 561</td>

Example 2: Synthesis of MOF-5 with water removal

The synthesis of Example 1 is repeated. This time, however, the vapors formed during the reaction are removed with a gentle stream of nitrogen over a distillation bridge. After filtration, the stock solution contains only about 0.5% H2O. The subsequent treatment of the samples occurs again analogously to Example 1.

The following surface values ​​are determined (according to Langmuir):

<td>Sample</td><td>Surface [m²/ g]</td>

<td>I (MH 166)</td><td> 3372</td>

<td>J (MH 167)</td><td> 3545</td>

<td>K (MH 170)</td><td> 2940</td>

<td>L (MH 183)</td><td> 3511</td>

<td>M (MH 184)</td><td> 3628</td>

<td colspan="2">Average 3399 ± 273</td>

ES 2 349 337 T3

The results show that due to the elimination of water from the reaction mixture, a structural material with a higher specific surface can be obtained and that a lower standard deviation results in the repetition of the tests, which indicates a higher reproducibility.

Example 3: Synthesis of MOF-5 with removal of water

The synthesis of Example 1 is repeated, however this time in the presence of 200 g of a recently activated 3A molecular sieve. After filtration the stock solution contains only about 0.34% H2O. The subsequent treatment of the samples occurs again analogously to Example 1. The samples exhibited an N2 surface (according to Langmuir) of 3182 m²/ g.