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The invention relates to a titanium based polycarboxylate inorganic-organic hybrid solid material that has a pseudo-cubic crystalline structure, to a method for preparing the same using a solvo-thermal procedure, and to the uses thereof in particular for the storage of gases, the adsorption of liqui

The invention relates to a titanium based polycarboxylate inorganic-organic hybrid solid material that has a pseudo-cubic crystalline structure, to a method for preparing the same using a solvo-thermal procedure, and to the uses thereof in particular for the storage of gases, the adsorption of liquids, the separation of liquids or gases, and the applications thereof in optics or catalysis, in the biomedical (controlled release drug), cosmetic fields, etc.

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1. An inorganic-organic hybrid solid material based on titanium, wherein said inorganic-organic hybrid solid material has a pseudo-cubic crystalline structure and that it is constituted exclusively of units of formula (I) below: TiaOb(OH)c[(−OOC)—X-#]d  (I)in which: X is an organic spacer and repres

1. An inorganic-organic hybrid solid material based on titanium, wherein said inorganic-organic hybrid solid material has a pseudo-cubic crystalline structure and that it is constituted exclusively of units of formula (I) below: TiaOb(OH)c[(−OOC)—X-#]d  (I)in which: X is an organic spacer and represents a saturated or unsaturated, linear or branched, aliphatic chain having 2 to 12 carbon atoms; a monocyclic, bicyclic or tricyclic hydrocarbon-based aromatic group that is unsubstituted or that is substituted by one or more substituents independently chosen from a halogen atom and amino, nitro, hydroxyl, C1-C4 trifluoroalkyl and C1-C4 alkyl groups; a benzophenone group; a monocyclic or bicyclic heteroaromatic group in which the ring(s) is(are) 5- or 6-membered ring(s), said group containing at least one heteroatom chosen from nitrogen and sulfur and being unsubstituted or substituted by one or more substituents R independently chosen from a halogen atom and amino, nitro, hydroxyl, C1-C4 trifluoroalkyl and C1-C4 alkyl groups;a and b, which are identical or different, are integers varying from 1 to 16 inclusively;c and d, which are identical or different, are integers varying from 1 to 32 inclusively;the indices a, b, c and d adhere to the relation 4a=2b+c+d;the titanium atoms form a purely inorganic elementary building block constituted of titanium oxo complexes;# is the point through which two units of formula (I) are joined together; # represents a covalent bond between a carbon atom belonging to the spacer X and the carbon atom of a carboxylate group COO− of another unit of formula (I) and in which the two oxygen atoms of the carboxylate group belong respectively to two adjacent octahedral titanium oxo complexes of an elementary building block of said other unit of formula (I);said units of formula (I) together forming a three-dimensional structure and defining cavities having a free diameter of 4 to 40 Å that are accessible through triangular apertures having dimensions of 4 to 15 Å. 2. The material as claimed in claim 1, wherein the aliphatic chains defined for X are selected from the group consisting of C1-C1 alkyl chains and C2-C4 alkene or alkene chains. 3. The material as claimed in claim 1, wherein the hydrocarbon-based groups defined for X are selected from the group consisting of phenylene; chlorophenylene; bromophenylene; aminophenylene; nitrophenylene; mono-, di- or tetramethylphenylene: mono- or diethenylphenylene; mono- or dihydroxyphenylene; biphenylene; diphenyldiazene; naphthalene and anthracene groups. 4. The material as claimed in claim 1, wherein the heterocycles defined for X are selected from the group consisting of thiophene, bithiophene, pyridine, bipyridine and pyrazine rings. 5. The material as claimed in claim 1, wherein the subunit [−OOC—X-#] is selected from the groups of formulae (II-1) to (II-13) consisting of: in which: R is a halogen atom, an amino, nitro, hydroxyl, C1-C4 trifluoroalkyl or C1-C4 alkyl group;m is an integer ranging from 0 to 4;n is an integer ranging from 0 to 8;p is an integer ranging from 0 to 6;q is an integer ranging from 0 to 2; andr is an integer ranging from 0 to 3. 6. The material as claimed in claim 5, wherein the subunit [−OOC—X-#] is selected from the group consisting of phenyl-1-carboxylate, phenyl-2-amino-1-carboxylate, phenyl-2,5-dihydroxy-1-carboxylate and thiophene-2-carboxylate. 7. The material as claimed in claim 1, wherein the units of formula (I) are selected from the subunits of formula (I-1) consisting of: Ti8O8(OH)4 [(−OOC)—X-#]12  (I-4)in which: X and # are as defined above in claim 1;the titanium atoms form a purely inorganic elementary building block constituted of 8 octahedral titanium oxo complexes each comprising a central titanium atom surrounded by 6 oxygen atoms, said octahedral titanium oxo complexes being joined together either by a common edge, or by a common apex, in both cases by means of oxo-O— or hydroxo-OH— bridges; said building blocks being connected together in the three dimensions of space by organic spacers X; it being understood that each of the building blocks is connected to 12 organic spacers by means of carboxylate groups COO− in which each of the two oxygen atoms is an integral part of two adjacent titanium oxo complexes. 8. The material as claimed in claim 1, wherein the cavities have a tree diameter of 5 to 12.6 Å. 9. The material as claimed in claim 1, wherein said material has a BET specific surface area of 200 to 6000 m2/g. 10. The material as claimed in claim 1, wherein said material has a pore volume of 0.1 to 3 cm3/g. 11. The use of a material as defined in claim 1, as a catalyst support for carrying out heterogeneously catalyzed chemical reactions or as a gas storage/separation/purification material or as a matrix for encapsulating active principles (medicaments, cosmetics) or else as a photochromic material for information storage, laser printing or as an oxygen indicator. 12. A process for preparing an inorganic-organic hybrid solid material based on titanium as defined in claim 1, wherein said process comprises the following steps: 1) in a first step, a reaction mixture is prepared comprising: i) at least one titanium precursor chosen from titanium alkoxides of formula below: Ti(OR1)4  (III)in which R1 is a linear or branched alkyl radical comprising from 1 to 4 carbon atoms or at least one titanium oxo complex of formula (IV) below: TixOy(OR2)z(OOCR3)w  (IV)in which: R2 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical or a phenyl ring optionally substituted by one or more radicals chosen from a halogen atom, C1-C4 alkyl and C2-C3 alkene radical;R3 represents a linear or branched C1-C4 alkyl radical, a C1-C4 trihaloalkyl radical or a phenyl ring;x is an integer ranging from 2 to 18:y is an integer ranging from 1 to 27;z is an integer ranging from 0 to 32;w is an integer ranging from 0 to 16;and in which the titanium atoms form an elementary building Hock constituted of a purely inorganic core of titanium oxo complexes in octahedral coordination each comprising a central titanium atom surrounded by 6 oxygen atoms, said octahedral titanium oxo complexes being joined together either by a common edge, or by a common apex, in both cases by means of oxo-O— or hydroxo-OH-bridges; said building blocks being surrounded by organic ligands of alcoholate (OR2) and/or carboxylate (OOCR3) type;ii) at least one dicarboxylic acid of formula (V) below: HOOC—X′—COOH  (V)in which X′ represents a saturated or unsaturated, linear or branched, aliphatic chain having from 2 to 12 carbon atoms, a benzophenone group or a monocyclic, bicyclic or tricyclic hydrocarbon-based aromatic group that is unsubstituted or that is substituted by one or more substituents R′ independently chosen from a halogen atom and amino, nitro, hydroxyl, C1-C4 trifluoroalkyl and C1-C4 alkyl groups;iii) a mixture of at least two organic solvents comprising at least one solvent S1 chosen from C1-C4 alcohols, benzyl alcohol and chlorobenzyl alcohol, and at least one solvent S2 selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide, ethylene dioxane, acetonitrile, acetone, tetrahydrofuran, pyridine and N-methylpyrrolidone;2) in a second step, the reaction mixture thus obtained is brought to a temperature of 70 to 200° C., for 4 to 72 hours, until a precipitate corresponding to the expected solid material is obtained; then3) in a third step, the reaction mixture is cooled to ambient temperature;4) in a fourth step, the solid material is separated from the mixture of organic solvents;it being understood that when the solid material is constituted of units of formula (I) in which X is a monocyclic or bicyclic heteroaromatic group in which the ring(s) is(are) optionally substituted 5- or 6-membered ring(s), said group containing at least one heteroatom selected from the group consisting of nitrogen and sulfur, then said process also comprises the following additional steps:5) a fifth step of preparing a dispersion of the solid material resulting from the fourth step in at least one polar organic solvent, in the presence of at least one dicarboxylic acid of formula (VI) below: HOOC—X″—COOH  (VI)in which X″ represents a monocyclic or bicyclic heteroarornatic group in which the ring(s) is(are) 5- or 6-membered ring(s), said group containing at least one heteroatom selected from the group consisting of nitrogen and sulfur and being unsubstituted or substituted by one or more substituents R independently selected from the group consisting of a halogen atom and amino, nitro, hydroxyl, C1-C4 trifluoroalkyl and C1-C4 alkyl groups;6) a sixth step, during which the dispersion thus obtained is brought to a temperature of 100 to 150° C. for a time of 4 hours to 4 days, which leads to the formation of a precipitate corresponding to the expected solid material; then7) a seventh step during which the temperature is allowed to return to ambient temperature; and8) an eighth step of separating the solid material thus obtained from the organic solvent(s). 13. The process as claimed in claim 12, wherein the precursors of formula (III) are selected from the group consisting of titanium ethoxide, titanium isopropoxide, titanium n-propoxide and titanium butoxide. 14. The process as claimed in claim 12, wherein the titanium oxo complexes of formula (IV) are chosen from Ti16O16(OCH2CH3)32 and Ti8O8(OOCR3)16 in which R3 is as defined in claim 12. 15. The process as claimed in claim 12, wherein the dicarboxylic acid of formula (V) is selected from the group consisting of benzene-1,4-dicarboxylic acid, 2-aminobenzene-1,4-dicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, 2-chlorobenzene-1,4-dicarboxylic acid, 2-bromobenzene-1,4-dicarboxylic acid, 2,5-dihydroxybenzene-1,4-dicarboxylic acid, 2-methylbenzene-1,4-dicarboxylic acid, 2,5-dimethylbenzene-1,4-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenyl-3,3′-dicarboxylic acid, 4,4′-(diazene-1,2-diyl)dibenzoic acid, 3,3′-(diazene-1,2-diyl)dibenzoic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, 1,4-phenylenediacetic acid, 1,4-phenylenediacrylic acid and 4,4′-benzophenonedicarboxylic acid. 16. The process as claimed in claim 15, wherein the dicarboxylic acid of formula (V) is selected from the group consisting of benzene-1,4-dicarboxylic acid, 2,5-dihydroxybenzene-1,4-dicarboxylic acid and 2-aminobenzene-1,4-dicarboxylic acid. 17. The process as claimed in claim 11, wherein within the reaction mixture, the titanium alkoxide of formula (III) or titanium oxo complex of formula (IV)/dicarboxylic acid of formula (V) molar ratio varies from 0.1 to 2. 18. The process as claimed in claim 11, wherein the polar solvents used during the fifth step are chosen from mixtures of at least two organic solvents S1 and S2 comprising at least one solvent S1 selected from the group consisting of C1-C4 alcohols, benzyl alcohol and chlorobenzyl alcohol, and at least one solvent S2 selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide, ethylene glycol, dioxane, acetonitrile, acetone, tetrahydrofuran, pyridine and N-methylpyrrolidone. 19. The process as claimed in claim 11, wherein the dicarboxylic acids of formula (VI) are selected from the group consisting of thiophene-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid and pyrazine-2,6-dicarboxylic acid. 20. The process as claimed in claim 11, wherein the solid material resulting from the fourth step/dicarboxylic acid of formula (VI) molar ratio during the fifth step varies from 1 to 20.