US 2010.0076220A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0076220 A1 Schubert et al. (43) Pub. Date: Mar. 25, 2010

(54) NOVEL METAL, ORGANIC FRAMEWORKS (30) Foreign Application Priority Data BASED ON ALUMINUM, IRON AND CHROMUM Apr. 24, 2007 (EP) ...... O71068O2.7

(75) Inventors: Markus Schubert, Ludwigshafen Publication Classification (DE); Ulrich Mueller, Neustadt (DE); Stefan Marx, Zuerich (CH) (51) Int. Cl. CD7C 63/26 (2006.01) Correspondence Address: OBLON, SPIVAK, MCCLELLAND MAIER & (52) U.S. Cl...... 562/.480 NEUSTADT, L.L.P. 194O DUKE STREET ALEXANDRIA, VA 22314 (US) (57) ABSTRACT (73) Assignee: BASF SE, Ludwigshafen (DE) The present invention relates to a porous metal organic frame work comprising a bidentate organic compound coordinated (21) Appl. No.: 12/597.616 to a metalion selected from the group of metals consisting of (22) PCT Fled: Apr. 23, 2008 Al, Fe and Cr, with the bidentate organic compound being derived from a dicarboxylic acid, wherein the framework has (86) PCT NO.: PCT/EP2008/054887 a structure whose projection along has a pattern in which each side of a hexagon is bounded by a triangle. The present S371 (c)(1), invention further relates to shaped bodies and a process for (2), (4) Date: Dec. 4, 2009 preparing the porous metal organic framework and its use.

Patent Application Publication Mar. 25, 2010 Sheet 1 of 2 US 2010/0076220 A1

Fig.

Patent Application Publication Mar. 25, 2010 Sheet 2 of 2 US 2010/0076220 A1

US 2010/0076220 A1 Mar. 25, 2010

NOVEL METAL, ORGANIC FRAMEWORKS 0012. The object is achieved by a porous metal organic BASED ON ALUMINUM, IRON AND framework comprising a bidentate organic compound coor CHROMUM dinated to a metal ion selected from the group of metals consisting of Al, Fe and Cr, with the bidentate organic com pound being derived from a diacarboxylic acid, wherein the 0001. The present invention relates to porous metal framework has a structure whose projection along 001 has a organic frameworks, shaped bodies comprising these and a pattern in which each side of a hexagon is bounded by a process for preparing them and their use. triangle. 0002 Porous metal organic frameworks are known from 0013 The object is likewise achieved by a process for the prior art. They are notable, in particular, for their porosity preparingaporous metal organic framework according to the and can frequently be employed in applications comparable invention, which comprises the step to those known for inorganic Zeolites. 0014 reaction of a reaction mixture comprising at least 0003 Metal organic frameworks usually comprise an at one compound of a metal selected from the group con least bidentate organic compound which is coordinated to a sisting of Al, Fe and Crand the bidentate organic com metal ion and together with the metalion forms the skeleton pound or a salt thereof in the presence of an auxiliary of the metal organic framework. having at least one deprotonatable group in an organic 0004. Appropriate choice of metal and/or organic com Solvent at a predetermined temperature and a predeter pound makes optimization for the desired field of application mined pressure. 0015. It has been found that the above-described produc possible. Here, for example, the choice of organic compound tion process using an auxiliary forms novel metal organic can exert an influence on the pore distribution. In addition, the frameworks which have a structure different from the con metal can make a contribution in adsorption processes. ventionally prepared known structures made up of the same 0005. However, reaction conditions in the preparation of metals and organic compounds. metal organic frameworks and auxiliaries used in the reaction 0016. In particular, it has surprisingly been found that in can also influence the framework structure. the presence of an auxiliary a structure known as “MIL-68 0006 Thus, for example, zeolite-like metal organic frame for V'-comprising metal organic frameworks is formed, works are produced by Y. Liu et al., Chem. Commun. 14 with the structure being obtained spontaneously in these (2006), 1488-1490, with the aid of structure-directing agents. frameworks. Vanadium terephthalate is described by K. Bar Further Such frameworks are described in WO-A 2006/ thelet et al., Chem. Commun. 2004, 520-521. Here, a struc 116340. ture whose projection along 001 has a pattern in which each 0007. There is thus a continual need to provide specific side of a hexagon is bounded by a triangle is found. metal organic frameworks which have, in particular, extraor 0017. The present invention is described in more detail dinary properties which are attributable to, in particular, spe below. cific preparative methods. 0018 FIG. 1 schematically shows the above-described 0008. An interesting metal is aluminum since compara pattern, with the octahedra depicted in FIG.1 representing the tively robust metal organic frameworks can be obtained octahedrally coordinated metal centers. because of strong coordinate bonds. In addition, because of (0019 FIG. 2 shows the X-ray diffraction pattern of the its octahedral coordination, the Al" ion is in principle suit aluminum terephthalate of the invention. The intensity I(Ln able for building up three-dimensional frameworks. Further (Counts)) is shown here as a function of the 2-theta scale more, the salts of aluminum which can be used as starting (20). materials are readily available and inexpensive. Owing to 0020 FIG. 3 shows curves for the adsorption of carbon their similar structure, metal organic frameworks based on dioxide and carbon monoxide on an aluminum terephthalate iron and chromium are also of interest in addition to those framework according to the invention and an aluminum based on aluminum. terephthalate framework known from the prior art. 0009. A particularly interesting metal organic framework 0021 FIG. 1 shows the above-described pattern purely is aluminum terephthalate. This is described by T. Loiseau et schematically. A more detailed depiction is shown in FIG. 2 al., Chem. Eur. J. 10 (2004), 1373-1382. A conventional on page 520 of K. Barthelet et al., Chem. Commun. 2004, preparation gives a base structure in which parallel —Al 520-521. (OH)—Al-(OH)— chains are crosslinked into the second 0022 Particularly the case of aluminum terephthalate, the and third dimension of the dicarboxylic linker, so that they structure of the corresponding porous metal organic frame span one-dimensional channels having a diamond-shaped work of the invention can be recognized by the X-ray diffrac cross section. The base structure is known in the literature as tion pattern (XRD) having a main reflection in the range “MIL-53”. The crystal system is, (in the dry “ht” form) 4°<20<6°, preferably in the range 4.5°.<20<5.5°. orthorhombic and the space group is Imma. The same struc 0023. Here, the diffraction pattern can be determined as ture is produced in the conventional preparation of iron follows: the sample is installed as powder in the sample terephthalate and chromium terephthalate (T. R. Whitfield et container of a commercially available instrument (Siemens al., Solid State Sciences 7 (2005), 1096-1 103: S. Bourrelly et D-5000 diffractometer or Bruker D8-Advance). As radiation al., J. Am. Chem. Soc. 127 (2005), 13519-13521). Source, use is made of Cu-KC. radiation using variable pri 0010 Despite the known metal organic frameworks, there mary and secondary orifice plates and a secondary monochro is a need for alternative frameworks which have superior mator. The signal is detected by means of a Scintillation properties, especially in respect of the storage and separation detector (Siemens) or a Solex semiconductor detector of gases. (Bruker). The measurement range for 20 is typically from 2 0011. It is therefore an object of the present invention to to 70°. The angle step is 0.02° and the measurement time per provide Such frameworks and a process for preparing them. angle step is typically from 2 to 4 seconds. In the evaluation, US 2010/0076220 A1 Mar. 25, 2010 reflections are distinguished from the background noise by an 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, at least 3-times higher signal strength. An area analysis can be phenylindandicarboxylic acid, 1,3-dibenzyl-2-oxoimidazoli carried out manually by drawing a baseline for the individual dine-4,5-dicarboxylic acid, 1.4-cyclohexanedicarboxylic reflections. As an alternative, programs such as “Topas-Pro acid, naphthalene-1,8-dicarboxylic acid, 2,-benzoylbenzene file' from Bruker can be used, in which case the fitting to the 1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5- background is preferably carried out automatically by means cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic of a 1st order polynomial in the software. acid, pyridine-3,4-dicarboxylic acid, 3.6.9-trioxaunde 0024. The structure of the aluminum terephthalate frame canedicarboxylic acid, hydroxybenzophenonedicarboxylic work of the invention has an orthorhombic unit cell and has acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicar the space group Cmcm. boxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4- 0025. The abbreviations used for the space groups are dicarboxylic acid, 2.3-pyrazinedicarboxylic acid, 5,6-dim known to those skilled in the art and are standardized. Refer ethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diamino(diphenyl ence may be made, for example, to the Internet page of the ether)diimidedicarboxylic acid, 4,4'-diaminodiphenyl International Union of Crystallography (http://www.iucr.org/ methanediimidedicarboxylic acid, 4,4'-diamino(diphenyl iucr-top/it/index.html). Sulfone)diimidedicarboxylic acid, 1,4-naphthalenedicar 0026. The metal component of the framework of the boxylic acid, 2,6-naphthalenedicarboxylic acid, 1.3-adaman present invention is selected from the group of metals con taneedicarboxylic acid, 1.8-naphthalenedicarboxylic acid, sisting of Al, Fe and Cr. Preference is given to A1. Particular 2.3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphtha mention should here be made of the trivalentions. lenedicarboxylic acid, 8-nitro-2,3-naphthalenecarboxylic 0027. In addition, the metal organic framework of the acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene invention comprises a bidentate organic compound derived 2,3-dicarboxylic acid, 2',3'-diphenyl-p-terphenyl-4,4'-dicar from a dicarboxylic acid. boxylic acid, (diphenyl ether)-4,4'-dicarboxylic acid, imida Zole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2.8- 0028. For the purposes of the present invention, the term dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, "derived means that the bidentate organic compound is 7,8-quinolinedicarboxylic acid, 4.5-imidazoledicarboxylic present in partly deprotonated or completely deprotonated acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontane form or as a Sulfur analogue in which one or both carboxylic dicarboxylic acid, tetradecanedicarboxylic acid, 1.7-heptadi acid functions have been replaced by the functional group carboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, —C(=O)SH or its tautomer or C(=S)SH in the framework. 2,5-dihydroxy-1,4-dicarboxylic acid, pyrazine-2,3-dicar Furthermore, the bidentate organic compound can comprise boxylic acid, furan-2,5-dicarboxylic acid, 1-nonen-6,9-dicar further substituents such as —OH, -NH2, —OCH, CH, boxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxy —NH(CH), N(CH), —CN and halides. diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl 0029. For example, the bidentate organic compound is 9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, derived from a dicarboxylic acid Such as Oxalic acid, Succinic 2.5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butene acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro dicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1.6- 3-methylduinoline-6,8-dicarboxylic acid, 2,4-dichloroben hexanedicarboxylic acid, decanedicarboxylic acid, 1.8-hep Zophenon-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic tadecanedicarboxylic acid, 1.9-heptadecanedicarboxylic acid, 2.6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-di acid, heptadecanedicarboxylic acid, acetylenedicarboxylic carboxylic acid, 1-benzyl-1H-pyrrol-3,4-dicarboxylic acid, acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic anthraquinone-1,5-dicarboxylic acid, 3.5-pyrazoledicar acid, 2.3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxy boxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane lic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedi 1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, carboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4- 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane dicarboxylic acid, 2-methylduinoline-3,4-dicarboxylic acid, 2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxy or camphordicarboxylic acid. lic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-di amino-phenylmethane-3,3'-dicarboxylic acid, quinoline-3,4- 0030 The at least bidentate organic compound is more dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2.8- preferably one of the dicarboxylic acids mentioned by way of dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6- example above as such. dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, 0031 Particular preference is given to aromatic dicar thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5- boxylic acids having from 6 to 14 ring atoms which can be dicarboxylic acid, tetrahydropyran-4.4-dicarboxylic acid, carbon or nitrogen. However, the ring preferably does not perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, have any heteroatoms. The at least one organic compound is Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxy particularly preferably derived from a benzenedicarboxylic lic acid, 3.5-cyclohexadiene-1,2-dicarboxylic acid, octa-di or naphthalenedicarboxylic acid. In particular, the compound carboxylic acid, pentane-3.3-carboxylic acid, 4,4'-diamino is at least one of these dicarboxylic acids as such. 1,1'-biphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl 0032 Particular mention may here be made of 1,2-ben 3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4- Zenedicarboxylic acid (phthalic acid), 1,3-benzenedicar bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'- boxylic acid (isophthalic acid), 1,4-benzenedicarboxylic acid binaphthyldicarboxylic acid, 7-chloro-8-methylduinoline-2, (terephthalic acid), 2,6-naphthalenedicarboxylic acid, 1,4- 3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'- naphthalenedicarboxylic acid and 1.5-naphthalenedicar dicarboxylic acid, polytetrahydrofuran 250-dicarboxylic boxylic acid as dicarboxylic acid. Very particular preference acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic is given to terephthalic acid. acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy) 0033. A particularly preferred metal organic framework phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, according to the invention is aluminum terephthalate. US 2010/0076220 A1 Mar. 25, 2010

0034. The metal organic framework according to the 0050. The kneading and/or shaping is, in a further embodi invention can be present in powder form or as agglomerate. ment, carried out with addition of at least one binder which 0035. The porous metal organic framework according to can in principle be any chemical compound which ensures a the invention can be used as such in powder form or is con Viscosity of the composition to be kneaded and/or shaped verted into a shaped body. which is desired for kneading and/or shaping. Accordingly, 0036. Accordingly, a further aspect of the present inven binders can, for the purposes of the present invention, be tion provides for the porous metal organic framework of the either viscosity-increasing or viscosity-reducing compounds. invention to be present as powder. 0051 Preferred binders are, for example, aluminum oxide 0037. A further aspect of the present invention is accord or binders comprising aluminum oxide, as described, for ingly a shaped body comprising the porous metal organic example, in WO94/29408, silicon dioxide, as described, for framework of the invention. example, in EP 0592050A1, mixtures of silicon dioxide and 0038. The production of shaped bodies comprising metal aluminum oxide, as described, for example, in WO94/13584, organic frameworks is described, for example, in WO-A clay minerals as described, for example, in JP 03-037156 A. O3F102OOO. for example montmorillonite, kaolin, bentonite, halloysite, 0039 Preferred methods of producing shaped bodies are dickite, nacrite and anauxite, alkoxysilanes as described, for extrusion or tableting. In the production of shaped bodies, the example, in EP 0102544 B1, for example tetraalkoxysilanes framework can be admixed with further materials such as Such as tetramethoxysilane, tetraethoxysilane, tetra binders, lubricants or other additives which are added during propoxysilane, tetrabutoxysilane, or, for example, trialkox production. It is likewise conceivable for the framework to ysilanes such as trimethoxysilane, triethoxysilane, tripro have further constituents such as absorbents such as activated poxysilane, tributoxysilane, alkoxytitanates, for example carbon or the like. tetralkoxytitanates Such as tetramethoxytitanate, tetraethox 0040. The possible geometries of the shaped bodies are ytitanate, tetrapropoxytitanate, tetrabutoxytitanate, or, for Subject to essentially no restrictions. Examples of shapes are, example, trialkoxytitanates, such as trimethoxytitanate, tri interalia, pellets such as circular pellets, pills, spheres, gran ethoxytitanate, tripropoxytitanate, tributoxytitanate, alkox ules, extrudates Such as rods, honeycombs, grids or hollow yZirconates, for example tetraalkoxyZirconates such as tet bodies. ramethoxy Zirconate, tetraethoxyZirconate, 0041. To produce these shaped bodies, all suitable pro tetrapropoxy Zirconate, tetrabutoxy Zirconate, or, for example, cesses are possible in principle. The following procedures are trialkoxyZirconates Such as trimethoxy Zirconate, triethox particularly preferred: yzirconate, tripropoxyzirconate, tributoxyzirconate, silica 0042 kneading?pan milling of the framework either Sols, amphiphilic Substances and/or graphite. alone or together with at least one binder and/or at least 0052. As viscosity-increasing compound, it is possible to one pasting agent and/or at least one template compound also use, if appropriate in addition to the abovementioned to give a mixture; shaping of the resulting mixture by compounds, for example, an organic compound and/or a means of at least one Suitable method such as extrusion; hydrophilic polymer such as cellulose or a cellulose deriva optional washing and/or drying and/or calcination of the tive Such as methylcellulose and/or a polyacrylate and/or a extrudate; optional finishing treatment. polymethacrylate and/or a polyvinyl alcohol and/or a polyvi 0043 Tableting together with at least one binder and/or nyl pyrrolidone and/or a polyisobutene and/or a polytetrahy another auxiliary. drofuran and/or a polyethylene oxide. 0044) Application of the framework to at least one 0053 As pasting agent, it is possible to use, inter alia, porous or nonporous Support material. The material preferably water or at least one alcohol Such as a monoalcohol obtained can then be processed further to produce a having from 1 to 4 carbon atoms, for example methanol, shaped body by the above-described method. ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, 0045 Application of the framework to at least one 2-methyl-1-propanol or 2-methyl-2-propanol or a mixture of porous or nonporous Substrate. water and at least one of the alcohols mentioned or a polyhy 0046 Kneading?pan milling and shaping can be carried dric alcohol Such as a glycol, preferably a water-miscible out by any Suitable method, as described, for example, in polyhydric alcohol, either alone or in admixture with water Ullmann's Enzyklopädie der Technischen Chemie 4, 4th edi and/or at least one of the monohydric alcohols mentioned. tion, volume 2, p. 313 ff. (1972). 0054 Further additives which can be used for kneading 0047. Kneading?pan milling and/or shaping can, for and/or shaping are, inter alia, amines or amine derivatives example, be carried out by means of a piston press, roller Such as tetraalkylammonium compounds or amino alcohols press in the presence or absence of at least one binder mate and carbonate-comprising compounds, e.g. calcium carbon rial, compounding, pelletization, tableting, extrusion, coex ate. Such further additives are described, for instance, in EPO trusion, foaming, spinning, coating, granulation, preferably 389 041 A1, EP 0200 260A1 or WO95/19222. spray granulation, spraying, spray drying or a combination of 0055. The order of addition of the additives such as tem two or more of these methods. plate compound, binder, pasting agent, viscosity-increasing 0048 Very particular preference is given to producing pel Substance in shaping and kneading is in principle not critical. lets and/or tablets. 0056. In a further preferred embodiment, the shaped body 0049. The kneading and/or shaping can be carried out at obtained after kneading and/or shaping is Subjected to at least elevated temperatures, for example in the range from room one drying step which is generally carried out at a temperature temperature to 300° C., and/or at superatmospheric pressure, in the range from 25 to 500°C., preferably in the range from for example in the range from atmospheric pressure to a few 50 to 500° C. and particularly preferably in the range from hundred bar, and/or in a protective gas atmosphere, for 100 to 350° C. It is likewise possible to carry out drying under example in the presence of at least one noble gas, nitrogen or reduced pressure or under a protective gas atmosphere or by a mixture of two or more thereof. spray drying. US 2010/0076220 A1 Mar. 25, 2010

0057. In a particularly preferred embodiment, at least one 0066. The process can be carried out in an undivided elec of the compounds added as additives is at least partly removed trolysis cell. Especially Suitable cells are gap cells or stacked from the shaped body during this drying process. plate cells. These can be connected in a bipolar fashion. 0058. The metal organic framework of the invention com Suitable reaction media are, for example, methanol, ethanol, prises pores, in particular micropores and/or mesopores. dimethylformamide, diethylformamide and mixtures of two Micropores are defined as pores having a diameter of 2 nm or or more of these solvents. less and mesopores are defined by a diameter in the range 0067 Furthermore, an electrolyte salt or a plurality of from 2 to 50 nm (Pure & Appl. Chem. 57 (1985) 603-619). electrolyte salts can be present in the reaction mixture. Here, The presence of micropores and/or mesopores can be the electrolyte salt can have a quaternary ammonium ion as checked by means of sorption measurements which deter cation component and an alkoxysulfate ion as anion compo mine the uptake capacity of the metal organic frameworks for nent. The total Solids content should be greater than or equal nitrogen as 77 kelvin (Langmuir method) in accordance with to 0.5% by weight. DIN 66131 and/or DIN 66.134. 0068. The reaction in the process of the invention for pre 0059. The specific surface area, calculated according to paring the metal organic framework of the invention can also the Langmuir model (DIN 66131, 66134), of the metal be carried out by a classical route. Here, the metal compound organic framework of the invention in powder form is pref is typically a metal salt. erably at least 1000 m/g, more preferably at least 1200 m/g, 0069. The metal salt can be in the form of an alkoxide, more preferably at least 1400 m/g, even more preferably at acetonate, halide, Sulfite, as Salt of an organic or inorganic, least 1600 m/g, even more preferably at least 1650 m/g. oxygen-comprising acid or a mixture thereof. 0060 Shaped bodies comprising the metal organic frame 0070 An alkoxide is, for example, a methoxide, ethoxide, work of the invention can have a lower specific Surface area; n-propoxide, i-propoxide, n-butoxide, i-butoxide, t-butoxide but preferably at least 500 m/g, more preferably at least 600 or phenoxide. m?g, even more preferably at least 700 m/g, in particular at 0071. An acetonate is, for example, acetylacetonate. least 800 m/g. 0072 A halide is, for example, chloride, bromide or 0061 The porous metal organic framework of the inven iodide. tion can be obtained by reaction of a reaction mixture com 0073. An organic, oxygen-comprising acid is, for prising at least one compound of a metal selected from the example, formic acid, acetic acid, propionic acid or another group consisting of Al, Fe and Cr and the bidentate organic alkylmonocarboxylic acid. compound or a salt thereof in the presence of an auxiliary 0074 An inorganic, oxygen-comprising acid is, for having at least one deprotonatable group. The reaction takes example, Sulfuric acid, Sulfurous acid, phosphoric acid or place in an organic solvent at a predetermined temperature nitric acid. and a predetermined pressure. 0075. The metal compound can, if appropriate, have water 0062. As organic component of the porous metal organic of hydration, which is preferred. framework of the invention, use is made of a dicarboxylic acid 0076 Particular preference is given to the hydrates of the which can be reacted with a metal compound. It is likewise chloride, nitrate and Sulfate as metal compound. possible to use derivatives of the dicarboxylic acid. Thus, for 0077. The process of the invention takes place in the pres example, it is conceivable to use the dicarboxylic acid in the ence of an auxiliary which has at least one deprotonatable form of its salt. The salt, in which the dicarboxylic acid is group. This is necessary in order to obtain the less thermody present as completely or partly deprotonated anion, can have namically favorable structure according to the invention for any Suitable cation. the metal organic frameworks of the invention rather than the 0063. Such cations can be, for example, monovalent or "MIL-53 structure known from the prior art. divalent, preferably monovalent, metalions. Examples are, in 0078 Suitable deprotonatable groups are, in particular, particular, sodium and potassium salts. It is likewise possible the hydroxy group, the amino group, the carboxyl group, the to use cations of ammonium compounds. Here, particular Sulfonic acid group, the phosphonic acid group. Here, the mention may be made of ammonium itself and also alkylam carboxylic acid and the Sulfonic acid group are preferred. monium cations. 007.9 The auxiliary preferably has at least one heteroatom 0064. The metal compound can be produced by anodic selected from the group consisting of nitrogen and Sulfur. In oxidation of the corresponding metal. In Such a case, the addition, preference is given to at least one aromatic Substrc porous metal organic framework of the invention is prepared ture being present. by an at least partly electrochemical route. Processes for the 0080. The auxiliary preferably has a molar mass in the electrochemical preparation of porous metal organic frame range from 140 to 1000 g/mol. The molar mass is more works are described in WO-A 2005/049892. The metal com preferably at least 200 g/mol, even more preferably at least pound for the porous metal organic framework of the inven 300 g/mol and in particular more than 400 g/mol. tion can also be produced in this way. I0081 Examples of suitable auxiliaries are 3,5-dihydroxy 0065. In the electrochemical preparation of the porous benzoic acid, 2,5-dihydroxybenzoic acid, mucic acid, metal organic framework of the invention, cathodic redepo glutamine, 4-sulformoylbenzoic acid, 2-mercaptonicotinic sition of the metalion is preferably at least partly prevented by acid, calconcarboxylic acid or SulfaSalazine. means of at least one of the following measures: I0082 Particular preference is given to calconcarboxylic (i) use of an electrolyte which promotes cathodic formation of acid and SulfaSalazine, in particular Sulfasalazine. hydrogen; I0083. The reaction in the process of the invention for pre (ii) addition of at least one compound which leads to cathodic paring the porous metal organic framework of the invention is depolarization; carried out at least in the presence of an organic solvent. (iii) use of a cathode having a suitable hydrogen overvoltage. Solvothermal conditions can be used here. US 2010/0076220 A1 Mar. 25, 2010

0084. For the purposes of the present invention, the term more preferably 5% by weight, even more preferably 1% by “thermal” refers to a production process in which the reaction weight, more preferably 0.1% by weight, particularly prefer to form the porous metal organic framework of the invention ably 0.01% by weight, based on the total weight of the sol is carried out in a pressure vessel which is closed during the Vent. reaction and is heated to an elevated temperature so that a 0097. The maximum water content during the reaction is pressure is built up within the reaction medium in the pressure preferably 10% by weight, more preferably 5% by weight and vessel as a result of the vapor pressure of the solvent present. even more preferably 1% by weight. 0085. The reaction is preferably not carried out in a water 0098. The term “solvent encompasses pure solvents and comprising medium and likewise not under Solvothermal mixtures of different solvents. conditions. 0099 Furthermore, the process step of reaction of the at I0086 Accordingly, the reaction in the process of the least one metal compound with the at least one bidentate invention is preferably carried out in the presence of a non organic compound is preferably followed by a calcination aqueous solvent step. The temperature set here is typically above 250° C., 0087. The reaction is preferably carried out at a pressure of preferably from 300 to 400° C. from 1 bar to 16 bar (absolute), preferably from 1 to 3 bar 0100. The calcination step enables the at least bidentate (absolute). However, the pressure is more preferably not more organic compound present in the pores to be removed. than 1230 mbar (absolute). In particular, the reaction takes 0101. In addition or as an alternative thereto, the removal place at atmospheric pressure. However, slightly Superatmo of the at least bidentate organic compound (ligand) from the spheric or Subatmospheric pressures can occur as a result of pores of the porous metal organic framework can be effected the apparatus. For the purposes of the present invention, the by treatment of the framework formed with a nonaqueous term "atmospheric pressure” means the actual atmospheric solvent. Here, the ligand is removed in a type of “extraction pressure +150 mbar. process and, if appropriate, replaced by a solvent molecule 0088. The reaction preferably takes place in a temperature in the framework. range from 100° C. to 200°C. The temperature is preferably 0102 The treatment is preferably carried out for at least 30 in the range from 110°C. to 170° C. The temperature is more minutes and can typically be carried out for up to 7 days. This preferably in the range from 120° C. to 150° C. can occur at room temperature or elevated temperature. It is 0089. The reaction mixture can further comprise a base. preferably carried out at elevated temperature, for example at This serves, in particular, to make the dicarboxylic acid least 40°C., preferably 60° C. Furthermore, the extraction readily soluble. The use of an organic solvent frequently preferably takes place at the boiling point of the solvent used makes it unnecessary to use such a base. Nevertheless, the (under reflux). solvent for the process of the invention can be selected so that 0103) The treatment can be carried out in a simple vessel it itself has a basic reaction, but this is not absolutely neces by slurrying and stirring the framework. It is also possible to sary for carrying out the process of the invention. use extraction apparatuses such as Soxhlet apparatuses, in 0090. It is likewise possible to use a base. However, pref particular industrial extraction apparatuses. erence is given to not using any additional base. 0104. As solvents, it is possible to use those mentioned 0091. It is also advantageous for the reaction to take place above, i.e., for example, C-alkanol, dimethyl Sulfoxide while stirring, which is also advantageous in the case of a (DMSO), N,N-dimethylformamide (DMF), N,N-diethylfor scale-up. mamide (DEF), N,N-dimethylacetamide (DMAc), acetoni 0092. The (nonaqueous) organic solvent is preferably a trile, toluene, dioxane, benzene, chlorobenzene, methyl ethyl C-alkanol, dimethylsulfoxide (DMSO), N,N-dimethylfor ketone (MEK), pyridine, tetrahydrofuran (THF), ethyl mamide (DMF), N,N-diethylformamide (DEF), N,N-dim acetate, optionally halogenated C-20o-alkane, Sulfolane, gly ethylacetamide (DMAc), acetonitrile, toluene, dioxane, ben col, N-methylpyrrolidone (NMP), gamma-butyrolactone, ali Zene, chlorobenzene, methyl ethyl ketone (MEK), pyridine, cyclic alcohols such as cyclohexanol, ketones such as acetone tetrahydrofuran (THF), ethyl acetate, optionally halogenated or acetylacetone, cycloketones such as cyclohexanone or Co-alkane, Sulfolane, glycol, N-methylpyrrolidone mixtures thereof. (NMP), gamma-butyrolactone, alicyclic alcohols such as 0105 Preference is given to methanol, ethanol, propanol, cyclohexanol, ketones such as acetone or acetylacetone, acetone, MEK and mixtures thereof. cycloketones Such as cyclohexanone, Sulfolene or mixtures 0106 A very particularly preferred extractant is methanol. thereof. 0.107 The solvent used for the extraction can be identical 0093. A C-alkanol is an alcohol having from 1 to 6 or different to that for the reaction of the at least one metal carbon atoms. Examples are methanol, ethanol, n-propanol, compound with the at least one at least bidentate organic i-propanol, n-butanol, i-butanol, t-butanol, pentanol, hexanol compound. In the “extraction’ it is not absolutely necessary and mixtures thereof. but preferred that the solvent is water-free. 0094. An optionally halogenated Coo-alkane is an 0108. The present invention further provides for the use of alkane which has from 1 to 200 carbon atoms and in which a porous metal organic framework according to the invention one or more up to all hydrogen atoms can be replaced by for the uptake of at least one substance for the purposes of its halogen, preferably chlorine or fluorine, in particular chlo storage, separation, controlled release, chemical reaction or rine. Examples are chloroform, dichloromethane, tetrachlo as Support. romethane, dichloroethane, hexane, heptane, octane and mix 0109 Theat least one substance is preferably a gas or a gas tures thereof. mixture. Liquids are also possible. 0.095 Preferred solvents are DMF, DEF, DMAcand NMP. 0110. In addition, the porous metal organic framework of Particular preference is given to DMF. the invention is Suitable for preparing the corresponding 0096. The term “nonaqueous' preferably refers to a sol metal oxides. Such transformations are described in the Inter vent which has a maximum water content of 10% by weight, national Application number PCT/EP2007/053571. Here, the US 2010/0076220 A1 Mar. 25, 2010

metal organic framework is heated to above its complete dioxide, the total pressure in the adsorber reactor concerned is decomposition temperature, so that the metal organic frame usually reduced to values in the range from 100 mbar to 1 bar. work which comprises the at least one metal ion forms the I0120 Preference is also given to the use of the framework metal oxide corresponding to the at least one metal ion or of the invention for the storage of a gas at a minimum pressure corresponding metal oxide mixtures. The specific Surface of 100 bar (absolute). The minimum pressure is more prefer area of the framework can advantageously be reproduced in ably 200 bar (absolute), in particular 300 bar (absolute). The the metal oxide (mixture). gas is in this case particularly preferably hydrogen or meth 0111. The present invention therefore further provides for al the use of a metal organic framework for preparing a corre 0.121. However, the at least one substance can also be a sponding metal oxide. For the purposes of the present inven liquid. Examples of such a liquid are disinfectants, inorganic tion, the term “metal oxide’ is used in the interests of sim or organic solvents, fuels, in particular gasoline or diesel, plicity even when a metal oxide mixture is present. hydraulic fluid, radiator fluid, brake fluid oran oil, in particu 0112 The uses according to the invention of the metal lar machine oil. The liquid can also be halogenated aliphatic organic framework apply analogously to shaped bodies com or aromatic, cyclic or acyclic hydrocarbons or mixtures prising the framework. thereof. In particular, the liquid can be acetone, acetonitrile, 0113 Processes for storage by means of metal organic aniline, anisol, benzene, benzonitrile, bromobenzene, frameworks in general are described in WO-A 2005/003622, butanol, tert-butanol, quinoline, chlorobenzene, chloroform, WO-A 2003/064030, WO-A 2005/049484, WO-A 2006/ cyclohexane, diethylene glycol, diethyl ether, dimethylaceta 089908 and DE-A 10 2005012087. The processes described mide, dimethylformamide, dimethyl Sulfoxide, dioxane, gla there can also be used for the metal organic framework of the cial acetic acid, acetic anhydride, ethyl acetate, ethanol, eth invention. Preferred gases for storage are methane and hydro ylene carbonate, ethylene dichloride, ethylene glycol, gen. ethylene glycol dimethyl ether, formamide, hexane, isopro 0114 Processes for separation or purification by means of panol, methanol, methoxypropanol, 3-methyl-1-butanol, metal organic frameworks in general are described in EP-A 1 methylene chloride, methyl ethyl ketone, N-methylforma 674 555, DE-A 10 2005 000938 and in the German patent mide, N-methylpyrrolidone, nitrobenzene, nitromethane, application number DE-A 10 2005 022 844. The processes piperidine, propanol, propylene carbonate, pyridine, carbon described there can also be used for the metal organic frame disulfide, sulfolane, tetrachloroethene, carbon tetrachloride, work of the invention. A gas which is preferably separated off tetrahydrofuran, toluene, 1,1,1-trichloroethane, trichloroeth is carbon dioxide, in particular from a gas mixture which ylene, triethylamine, triethylene glycol, triglyme, water or further comprises carbon monoxide. mixtures thereof. 0115 If the porous metal organic framework of the inven 0.122 Furthermore, the at least one substance can be an tion is used for storage, this is preferably carried out in a odorous Substance. temperature range from -200° C. to +80° C. A temperature I0123. The odorous substance is preferably a volatile range from -40°C. to +80°C. is more preferred. A preferred organic or inorganic compound which comprises at least one pressure range is from 20 bar to 1000 bar (absolute), in of the elements nitrogen, phosphorus, oxygen, Sulfur, fluo particular from 100 bar to 400 bar. rine, chlorine, bromine or iodine or is an unsaturated or aro 0116 For the purposes of the present invention, the terms matic hydrocarbon or a Saturated or unsaturated aldehyde or “gas' and “liquid” are used in the interests of simplicity, but a ketone. More preferred elements are nitrogen, oxygen, gas mixtures and liquid mixtures or liquid solutions are like phosphorus, Sulfur, chlorine, bromine; and particular prefer wise encompassed by the term “gas” or “liquid'. ence is given to nitrogen, oxygen, phosphorus and Sulfur. 0117 Preferred gases are hydrogen, natural gas, town gas, 0.124. In particular, the odorous Substance is ammonia, hydrocarbons, in particular methane, ethane, ethene, acety hydrogen Sulfide, Sulfur oxides, nitrogen oxides, oZone, lene, propane, n-butane and i-butane, carbon monoxide, car cyclic or acyclic amines, thiols, thioethers and aldehydes, bon dioxide, nitrogen oxides, oxygen, Sulfur oxides, halo ketones, esters, ethers, acids or alcohols. Particular prefer gens, halogenated hydrocarbons, NF, SF, ammonia, ence is given to ammonia, hydrogen Sulfide, organic acids boranes, phosphanes, hydrogen Sulfide, amines, formalde (preferably acetic acid, propionic acid, butyric acid, isobu hyde, noble gases, in particular helium, neon, argon, krypton tyric acid, Valeric acid, isovaleric acid, caproic acid, hep and Xenon. tanoic acid, lauric acid, pelargonic acid) and cyclic or acyclic 0118. The gas is particularly preferably carbon dioxide hydrocarbons comprising nitrogen or Sulfur and Saturated or which is separated off from a gas mixture comprising carbon unsaturated aldehydes such as hexanal, heptanal, octanal, dioxide. The gas mixture preferably comprises carbon diox nonanal, decanal, octenal or nonenal and in particular volatile ide together with at least H, CH or carbon monoxide. In aldehydes Such as butyraldehyde, propionaldehyde, acetalde particular, the gas mixture comprises carbon monoxide in hyde and formaldehyde and also fuels such as gasoline, diesel addition to carbon dioxide. Very particular preference is given (constituents). to mixtures which comprise at least 10 and not more than 45% 0.125. The odorous substances can also be fragrances by volume of carbon dioxide and at least 30 and not more than which are used, for example, for producing perfumes. 90% by volume of carbon monoxide. Examples of fragrances or oils which can release Such fra 0119) A preferred embodiment is pressure swing adsorp grances are: essential oils, basil oil, geranium oil, mint oil, tion using a plurality of parallel adsorber reactors, with the cananga oil, cardamom oil, lavender oil, peppermint oil, nut adsorbent bed being made up completely or partly of the meg oil, camomile oil, eucalyptus oil, Rosemary oil, lemon material according to the invention. The adsorption phase for oil, lime oil, orange oil, bergamot oil, muscatel Sage oil, the CO/CO separation preferably takes place at CO partial coriander oil, cypress oil, 1,1-dimethoxy-2-phenylethane, pressure of from 0.6 to 3 bar and a temperature of at least 20° 2,4-dimethyl-4-phenyltetrahydrofuran, dimethyltetrahy C., but not more than 70° C. To desorb the adsorbed carbon drobenzaldehyde, 2,6-dimethyl-7-octen-2-ol. 1,2-diethoxy US 2010/0076220 A1 Mar. 25, 2010

3,7-dimethyl-2,6-octadiene, phenylacetaldehyde, rose oxide, about 15° which are not observed in the conventional Al ethyl 2-methylpentanoate, 1-(2,6,6-trimethyl-1,3-cyclohexa terephthalate MOF (MIL-53). A novel structure is therefore dien-1-yl)-2-buten-1-one, ethyl vanillin, 2,6-dimethyl-2- present. The surface area is 1679 m/g. This is likewise higher octenol. 3,7-dimethyl-2-octenol, tert-butylcyclohexyl than the known surface area values for MIL-53 (up to 1500 acetate, anisyl acetate, allyl cyclohexyloxyacetate, ethyllina m/g). According to elemental analysis, the product com lool, eugenol, coumarin, ethyl acetoacetate, 4-phenyl-2,4,6- prises 11.6% by weight of Al, 44.2% by weight of carbon, trimethyl-1,3-dioxane, 4-methylene-3,5,6,6-tetramethyl-2- 2.8% by weight of hydrogen, 0.7% by weight of N and only heptanone, ethyl tetrahydrosafranate, geranyl nitrile, cis-3- 0.15% by weight of sulfur which originates as impurity from hexen-1-ol, cis-3-hexenyl acetate, cis-3-hexenyl methyl the auxiliary. carbonate, 2,6-dimethyl-5-hepten-1-al, 4-(tricyclo5.2.1.0 decylidene)-8-butanal, 5-(2,2,3-trimethyl-3-cyclopentenyl)- Example 2 3-methylpentan-2-ol. p-tert-butyl-alpha-methylhydrocinna maldehyde, ethyl5.2.1.0 tricyclodecanecarboxylate, Preparation of an Al-Terephthalic Acid MOF Using geraniol, citronellol, citral, linalool, linallyl acetate, ionone, Calconcarboxylic Acid as Auxiliary phenylethanol and mixtures thereof. (0.133 4.88 g of AlCl*6H2O, 5g of terephthalic acid and 0126 For the purposes of the present invention, a volatile 3.3 g of calconcarboxylic acid are suspended in 300 ml of odorous Substance preferably has a boiling point or boiling DMF in a glass flask. The mixture is heated to 130°C. while point range below 300° C. The odorous substance is more stirring and maintained under these conditions for 18 hours. preferably a readily Volatile compound or mixture. In particu The product obtained is filtered off and washed with 3x50 ml lar, the odorous Substance has a boiling point or boiling range of DMF and 4x50 ml of methanol. The product is subse below 250° C., more preferably below 230° C., particularly quently transferred to a paper thimble and extracted with preferably below 200° C. boiling methanol in an extraction apparatus for 120 hours. 0127 Preference is likewise given to odorous substances The product is finally dried at 110°C. in a vacuum drying which have a high volatility. The vapor pressure can be oven for 72 hours. The yield is 4.34g. employed as a measure of the volatility. For the purposes of I0134. The product displays the same reflections in the the present invention, a volatile odorous substance preferably X-ray diffraction pattern (XRD) as example 1. The surface has a vapor pressure of more than 0.001 kPa (20° C.). The area is 1594 m/g. According to elemental analysis, the prod odorous Substance is more preferably a readily Volatile com uct comprises 10.0% by weight of Al, 46.1% by weight of pound or mixture. The odorous Substance particularly pref carbon, 3.7% by weight of hydrogen, 3.2% by weight of N. erably has a vapor pressure of more than 0.01 kPa (20°C.), and only 0.07% by weight of sulfur. more preferably a vapor pressure of more than 0.05 kPa (20° C.). Particular preference is given to the odorous Substances Example 3 having a vapor pressure of more than 0.1 kPa (20° C.). 0128. Examples in which a chemical reaction can take Adsorption of CO and CO place in the presence of the metal organic framework of the I0135 Adsorptionisotherms for CO and CO, are measured invention are the alkoxylation of monools and polyols. The in the range from 0 to 1.2 bar on a sample of about 200 mg in method of carrying out Such alkoxylations is described in each case using the commercially available instrument ASAP WO-A03/035717 and WO-A 2005/03069. The porous metal 2420 (from Micromeritics). The measurement temperature is organic framework of the invention can likewise be used for 40° C. The samples are pretreated at 200° C. under vacuum epoxidation and for preparing polyalkylene carbonates and conditions (turbomolecular pump) for a number of hours hydrogen peroxide. Such reactions are described in WO-A before the measurement in each case. 03/101975, WO-A 2004/037895 and US-A 2004/081611. 0.136 FIG. 3 shows the respective isotherms in compari 0129 Particular preference is given to catalytic reactions. son with Al-terephthalic acid from the prior art. The figure 0130. In addition, the metal organic framework of the shows the gas uptake A (in standard ml/g) as a function of the invention can be used as Support, in particular as Support of a pressure p (in mbar). catalyst. 0.137 Samples measured are a sample as per example 1 (curve denoted by triangles: CO adsorption; curve denoted EXAMPLES by circles: CO adsorption in FIG. 3) and an Al-terephthalic Example 1 acid MOF having the “MIL-53 structure from the prior art prepared as described in example 12 of WO-A 2007/023 134 Preparation of an Al-Terephthalic Acid MOF Using (curve denoted by solid squares: CO adsorption, curve Sulfasalazine as Auxiliary denoted by open squares: CO adsorption in FIG. 3). 0131 4.88 g of AlCl*6HO, 5g of terephthalic acid and 0.138. The overall flatter adsorption isotherms for the 2.99g of sulfasalazine are suspended in 300 ml of DMF in a material according to the invention correlate with a lower glass flask. The mixture is heated to 130°C. while stirring and adsorption energy, so that less energy is required for regen maintained under these conditions for 18.5 hours. The prod eration of the material after adsorption (e.g. in the desorption uct obtained is filtered off and washed with 3x50 ml of DMF phase in a pressure Swing adsorption). In addition, the relative and 4x50 ml of methanol. The product is subsequently trans difference between the CO capacity and the CO capacity is ferred to a paper thimble and extracted with boiling methanol helpful since this corresponds to a higher selectivity and thus in an extraction apparatus for 120 hours. The product is finally higher achievable purities for a separation of CO from CO. dried at 100° C. in a vacuum drying oven for 24 hours. The 1. A porous metal organic framework comprising a biden yield is 4.12 g. tate organic compound coordinated to a metal ion selected 0132) The XRD (X-ray diffraction pattern) is shown in from the group consisting of Al, Fe and Cr, wherein the FIG. 2. Reflections are found at 20=about 5°, about 10° and bidentate organic compound is obtained by a dicarboxylic US 2010/0076220 A1 Mar. 25, 2010

acid; the framework has a structure of which projection along from the group consisting of Al, Fe and Crand the bidentate 001 has a pattern; and each side of a hexagon in the pattern organic compound or a salt thereof in the presence of an is bounded by a triangle. auxiliary having at least one deprotonatable group in an 2. The framework according to claim 1, wherein the metal organic solvent at a predetermined temperature and a prede is Al. termined pressure. 3. The framework according to claim 1, wherein the biden 8. The process according to claim 7, wherein the auxiliary tate organic compound is obtained by a benzenedicarboxylic has a molar mass in the range from 140 to 1000 g/mol. or naphthalenedicarboxylic acid. 9. The process according to claim 7, wherein the auxiliary 4. The framework according to claim 1, wherein the metal is 3,5-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, is Aland the bidentate organic compound is terephthalic acid. mucic acid, glutamine, 4-sulfamoylbenzoic acid, 2-mercap 5. The framework according to claim 4, wherein a X-ray tonicotinic acid, calconcarboxylic acid or Sulfasalazine. diffraction pattern of the framework has a main reflection in 10. (canceled) the range 4°-20<6°. 11. A method comprising uptaking at least one Substance 6. A shaped body comprising a porous metal organic by the metal organic framework according to claim 1. framework according to claim 1. 12. A method comprising uptaking at least one Substance 7. A process for preparing a porous metal organic frame by the shaped body according to claim 6. work according to claim 1, comprising reacting a reaction mixture comprising at least one compound of a metal selected c c c c c