The invention concern micro porous crystalline materials having large accessible global volume. T... more The invention concern micro porous crystalline materials having large accessible global volume. The special formulation of this material guarantees the mono dispersion of the pores dimensions, making them appropriate for the selective storage of guest molecules and for gas-separation. ADVANTAGES These materials presents an high capacity of reversible absorption of small gaseous molecules. The advantage of these compounds resides also in the simple and cheap preparation. Besides all the reactions occur in water solutions, avoiding the use of toxic organic solvents
Oxazolidinones fused to pyrazine or morpholine rings are prepared via aminocarboxylation reaction... more Oxazolidinones fused to pyrazine or morpholine rings are prepared via aminocarboxylation reaction of allyl amides of N-alkoxycarbonyl-protected α-amino acids in the presence of stoichiometric CuCl2.
The bicyclic ditopic linker 2,2'-biselenophene-5,5'-dicarboxylic acid (H2SpSp), specifica... more The bicyclic ditopic linker 2,2'-biselenophene-5,5'-dicarboxylic acid (H2SpSp), specifically designed for metal-organic framework (MOF) construction, has been synthesized in good yield and fully characterized. The corresponding zirconium MOF (Zr-MOF) [Zr6O4(OH)4(SpSp)3.8Cl4.4] (1; where missing linkers are replaced by chloride anions as shown by X-ray fluorescence and elemental analysis) is isostructural with its bithiophene and bithiazole analogues. Starting from 1, an extension of the biselenophene-based Zr-MOF family has been successfully achieved, exploiting the structural analogy of the five-membered heterocycles selenophene, thiophene, and thiazole. Thus, three mixed-linker MOFs containing variable amounts of different bis(heterocyclic) dicarboxylic acids have been prepared and fully characterized: the two double-mixed [Zr6O4(OH)4(SpSp)2.6(TpTp)1.3Cl4.2] (2; H2TpTp = 2,2'-bithiophene-5,5'-dicarboxylic acid) and [Zr6O4(OH)4(SpSp)2(TzTz)1.8Cl4.4] (3; H2TzTz = 2,2'-bithiazole-5,5'-dicarboxylic acid) materials, as well as the triple-mixed [Zr6O4(OH)4(SpSp)1.6(TpTp)1.2(TzTz)1.4Cl3.6] (4) compound. The four MOFs are luminescent under UV irradiation, exhibiting emission wavelengths falling in the blue-green visible region, as observed for their constitutive linkers. These materials open new horizons in the preparation of porous luminescent sensors or multicolor emitters for light-emitting diodes.
... [ 15 16. Kahn , O. , J. Kröber , C. Jay , 1992 . Adv. Mater. , 4 , 718 [CROSSREF] [CrossRef],... more ... [ 15 16. Kahn , O. , J. Kröber , C. Jay , 1992 . Adv. Mater. , 4 , 718 [CROSSREF] [CrossRef], [Web of Science ®] View all references 16 18. Gütlich , P. , Y. Garcia , HA Goodwin , 2000 . Chem. ... [ 26 33. Kröber , J. , E. Codjovi , O. Kahn , F. Grolière , C. Jay , 1993 . J. Am. Chem. Soc. ...
A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acid... more A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-R-oximinoamides. When three or more starting materials react in the same flask to produce a molecule which contains parts of all the reactants, a multicomponent reaction (MCR) takes place. 1 In general, MCRs stand out as a powerful tool for the rapid construction of quite complex molecules, not easily accessible via the classical two-component chemistry. 2 Among them, the Passerini reaction (Scheme 1) is the oldest MCR in which isocyanides have been used, 3 exploiting their propensity to react with nucleophiles and (4) (a) Marcaccini, S.
Three new fluorinated bis(pyrazoles), namely: 1,4-bis(1H-pyrazol-4-ylethynyl)-2-fluorobenzene (H2... more Three new fluorinated bis(pyrazoles), namely: 1,4-bis(1H-pyrazol-4-ylethynyl)-2-fluorobenzene (H2BPEFB), 1,4-bis(1Hpyrazol-4-ylethynyl)-2,3-difluorobenzene (H2BPEF2B) and 1,4-bis(1H-pyrazol-4-ylethynyl)-tetrafluorobenzene (H2BPEF4B) have been synthesized taking advantage of Sonogashira coupling reactions, and characterized as per their crystal and molecular structure, spectroscopic and dielectric properties, and hydrophobicity. In the crystal structures, the three molecules, whose deviation from planarity increases at increasing the fluorination degree, interact by means of hydrogen bonds, forming 2D supramolecular layers. Notably, the absorption and fluorescence emission properties are only slightly affected by the fluorination degree in both the solid state and solution. Furthermore, the spectral line-shapes are weakly dependent on the environment when dissolved in a number of solvents of different polarity and hydrogen-bonding affinity. On the other hand, the dielectric constant monotonically increases at increasing the number of fluorine atoms. In silico molecular modeling with the time-resolved density functional theory has offered a valuable mean to rationalize the above mentioned behaviors and has shed some light on the ligands affinity towards representative gases-H2O and CO2-and organic solvents-toluene.
A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acid... more A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-R-oximinoamides. When three or more starting materials react in the same flask to produce a molecule which contains parts of all the reactants, a multicomponent reaction (MCR) takes place. 1 In general, MCRs stand out as a powerful tool for the rapid construction of quite complex molecules, not easily accessible via the classical two-component chemistry. 2 Among them, the Passerini reaction (Scheme 1) is the oldest MCR in which isocyanides have been used, 3 exploiting their propensity to react with nucleophiles and (4) (a) Marcaccini, S.
An important goal in devising technologically relevant metal-organic frameworks (MOFs) lies in th... more An important goal in devising technologically relevant metal-organic frameworks (MOFs) lies in the synthesis of robust networks capable of withstanding sustained use under extreme conditions. Together with this feature, another important challenge in this field is the development of stable structures including functional pending groups, with the aim of tuning pore properties (size and shape, volume and decoration), possibly enhancing uptake capacity and selectivity toward a targeted guest. Along this line, we have recently demonstrated that, using linear or triangular polytopic pyrazolate-based bridging ligands, some of the most stable porous metal-organic structures ever prepared can be isolated, as a result of the strong metal-pyrazolate framework bonds.1 We have now prepared two large series of isostructural pyrazolate-based MOFs (bearing NO2, NH2, OH, SO3H functional groups), reminiscent of NiBDP and ZnBDP parent structures [H2BDP = 1,4-bis(1H-pyrazol-4-yl)benzene]. In this contribution, our recent results upon these two families of MOFs will be presented, which include the description of i) the pre-synthesis functionalization of the four tagged-ligands, ii) the solvothermal synthesis of the related MOFs and iii) their extensive structural characterization by means of variable temperature X-ray powder diffraction analysis. Finally, the relationships between the nature of the organic residues and the structural and functional properties (gas sorption and separation) of the resulted materials will be highlighted
The last years have witnessed a blooming of research interest on the preparation, characterizatio... more The last years have witnessed a blooming of research interest on the preparation, characterization and optimization of porous functional materials (MOFs, metalorganic frameworks) based on transition metal ions linked by long organic spacers in three dimensional networks [1]. The pioneering work of Yaghi\u2019s, Kitagawa\u2019s and F\ue9rey\u2019s groups in the synthesis of MOFs was initially based on porous metal polycarboxylates. In this context, several chemically stable and thermally inert porous systems have been isolated, their main drawback being, however, the easily hydrolysable nature of the M-carboxylate bond. Polyazolate systems, like pyrazolate and tetrazolate [2], offer a closely related stereochemistry to carboxylate and, at the same time, a higher basicity, possibly guaranteeing more robust coordinative bonds. Thus, planning to isolate new porous MOFs with long polytopic spacers possessing nitrogen donor sites, we turned our attention to the 1,4-(4-bispyrazolyl)benzene ligand (C12H10N4, H2bpb) [3]. Reacting the deprotonated form of the H2bpb moiety with nickel, copper and zinc salts, we isolated the highly porous homoleptic Ni(bpb) and Zn(bpb) species, and a dense Cu2(bpb) material. Ab-initio powder diffraction methods and thermodiffractometry allowed the determination of their crystal structures and flexibility. The different stereochemical requirements induce, in the 3-D Ni(II) and Zn(II) species, rhombic and square channels respectively, capable of hosting guest molecules and accounting for the 57 and 65% of the total volume. Indeed, both species possess permanent nanoporosity and adsorb large quantities of small gaseous molecules (N2, Ar at 77 K and CO2, CH4 at 273 K), as a consequence of their unusually large surface areas (peaking well above 2000 m2 g-1). The hydrophobic nature of the channels is also adequate for the incorporation of organic vapors (benzene, cyclohexane, 2,2-dimethylbutane) at 298 K, as witnessed by selectivity studies
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
The structural origin of the remarkable performance of the metal–organic framework Fe2(BPEB)3 as ... more The structural origin of the remarkable performance of the metal–organic framework Fe2(BPEB)3 as a CO2 adsorbent (40.5% of the host weight at 298 K and 10 bar) was investigated by combining advanced experimental and computational tools.
The invention concern micro porous crystalline materials having large accessible global volume. T... more The invention concern micro porous crystalline materials having large accessible global volume. The special formulation of this material guarantees the mono dispersion of the pores dimensions, making them appropriate for the selective storage of guest molecules and for gas-separation. ADVANTAGES These materials presents an high capacity of reversible absorption of small gaseous molecules. The advantage of these compounds resides also in the simple and cheap preparation. Besides all the reactions occur in water solutions, avoiding the use of toxic organic solvents
Oxazolidinones fused to pyrazine or morpholine rings are prepared via aminocarboxylation reaction... more Oxazolidinones fused to pyrazine or morpholine rings are prepared via aminocarboxylation reaction of allyl amides of N-alkoxycarbonyl-protected α-amino acids in the presence of stoichiometric CuCl2.
The bicyclic ditopic linker 2,2'-biselenophene-5,5'-dicarboxylic acid (H2SpSp), specifica... more The bicyclic ditopic linker 2,2'-biselenophene-5,5'-dicarboxylic acid (H2SpSp), specifically designed for metal-organic framework (MOF) construction, has been synthesized in good yield and fully characterized. The corresponding zirconium MOF (Zr-MOF) [Zr6O4(OH)4(SpSp)3.8Cl4.4] (1; where missing linkers are replaced by chloride anions as shown by X-ray fluorescence and elemental analysis) is isostructural with its bithiophene and bithiazole analogues. Starting from 1, an extension of the biselenophene-based Zr-MOF family has been successfully achieved, exploiting the structural analogy of the five-membered heterocycles selenophene, thiophene, and thiazole. Thus, three mixed-linker MOFs containing variable amounts of different bis(heterocyclic) dicarboxylic acids have been prepared and fully characterized: the two double-mixed [Zr6O4(OH)4(SpSp)2.6(TpTp)1.3Cl4.2] (2; H2TpTp = 2,2'-bithiophene-5,5'-dicarboxylic acid) and [Zr6O4(OH)4(SpSp)2(TzTz)1.8Cl4.4] (3; H2TzTz = 2,2'-bithiazole-5,5'-dicarboxylic acid) materials, as well as the triple-mixed [Zr6O4(OH)4(SpSp)1.6(TpTp)1.2(TzTz)1.4Cl3.6] (4) compound. The four MOFs are luminescent under UV irradiation, exhibiting emission wavelengths falling in the blue-green visible region, as observed for their constitutive linkers. These materials open new horizons in the preparation of porous luminescent sensors or multicolor emitters for light-emitting diodes.
... [ 15 16. Kahn , O. , J. Kröber , C. Jay , 1992 . Adv. Mater. , 4 , 718 [CROSSREF] [CrossRef],... more ... [ 15 16. Kahn , O. , J. Kröber , C. Jay , 1992 . Adv. Mater. , 4 , 718 [CROSSREF] [CrossRef], [Web of Science ®] View all references 16 18. Gütlich , P. , Y. Garcia , HA Goodwin , 2000 . Chem. ... [ 26 33. Kröber , J. , E. Codjovi , O. Kahn , F. Grolière , C. Jay , 1993 . J. Am. Chem. Soc. ...
A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acid... more A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-R-oximinoamides. When three or more starting materials react in the same flask to produce a molecule which contains parts of all the reactants, a multicomponent reaction (MCR) takes place. 1 In general, MCRs stand out as a powerful tool for the rapid construction of quite complex molecules, not easily accessible via the classical two-component chemistry. 2 Among them, the Passerini reaction (Scheme 1) is the oldest MCR in which isocyanides have been used, 3 exploiting their propensity to react with nucleophiles and (4) (a) Marcaccini, S.
Three new fluorinated bis(pyrazoles), namely: 1,4-bis(1H-pyrazol-4-ylethynyl)-2-fluorobenzene (H2... more Three new fluorinated bis(pyrazoles), namely: 1,4-bis(1H-pyrazol-4-ylethynyl)-2-fluorobenzene (H2BPEFB), 1,4-bis(1Hpyrazol-4-ylethynyl)-2,3-difluorobenzene (H2BPEF2B) and 1,4-bis(1H-pyrazol-4-ylethynyl)-tetrafluorobenzene (H2BPEF4B) have been synthesized taking advantage of Sonogashira coupling reactions, and characterized as per their crystal and molecular structure, spectroscopic and dielectric properties, and hydrophobicity. In the crystal structures, the three molecules, whose deviation from planarity increases at increasing the fluorination degree, interact by means of hydrogen bonds, forming 2D supramolecular layers. Notably, the absorption and fluorescence emission properties are only slightly affected by the fluorination degree in both the solid state and solution. Furthermore, the spectral line-shapes are weakly dependent on the environment when dissolved in a number of solvents of different polarity and hydrogen-bonding affinity. On the other hand, the dielectric constant monotonically increases at increasing the number of fluorine atoms. In silico molecular modeling with the time-resolved density functional theory has offered a valuable mean to rationalize the above mentioned behaviors and has shed some light on the ligands affinity towards representative gases-H2O and CO2-and organic solvents-toluene.
A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acid... more A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-R-oximinoamides. When three or more starting materials react in the same flask to produce a molecule which contains parts of all the reactants, a multicomponent reaction (MCR) takes place. 1 In general, MCRs stand out as a powerful tool for the rapid construction of quite complex molecules, not easily accessible via the classical two-component chemistry. 2 Among them, the Passerini reaction (Scheme 1) is the oldest MCR in which isocyanides have been used, 3 exploiting their propensity to react with nucleophiles and (4) (a) Marcaccini, S.
An important goal in devising technologically relevant metal-organic frameworks (MOFs) lies in th... more An important goal in devising technologically relevant metal-organic frameworks (MOFs) lies in the synthesis of robust networks capable of withstanding sustained use under extreme conditions. Together with this feature, another important challenge in this field is the development of stable structures including functional pending groups, with the aim of tuning pore properties (size and shape, volume and decoration), possibly enhancing uptake capacity and selectivity toward a targeted guest. Along this line, we have recently demonstrated that, using linear or triangular polytopic pyrazolate-based bridging ligands, some of the most stable porous metal-organic structures ever prepared can be isolated, as a result of the strong metal-pyrazolate framework bonds.1 We have now prepared two large series of isostructural pyrazolate-based MOFs (bearing NO2, NH2, OH, SO3H functional groups), reminiscent of NiBDP and ZnBDP parent structures [H2BDP = 1,4-bis(1H-pyrazol-4-yl)benzene]. In this contribution, our recent results upon these two families of MOFs will be presented, which include the description of i) the pre-synthesis functionalization of the four tagged-ligands, ii) the solvothermal synthesis of the related MOFs and iii) their extensive structural characterization by means of variable temperature X-ray powder diffraction analysis. Finally, the relationships between the nature of the organic residues and the structural and functional properties (gas sorption and separation) of the resulted materials will be highlighted
The last years have witnessed a blooming of research interest on the preparation, characterizatio... more The last years have witnessed a blooming of research interest on the preparation, characterization and optimization of porous functional materials (MOFs, metalorganic frameworks) based on transition metal ions linked by long organic spacers in three dimensional networks [1]. The pioneering work of Yaghi\u2019s, Kitagawa\u2019s and F\ue9rey\u2019s groups in the synthesis of MOFs was initially based on porous metal polycarboxylates. In this context, several chemically stable and thermally inert porous systems have been isolated, their main drawback being, however, the easily hydrolysable nature of the M-carboxylate bond. Polyazolate systems, like pyrazolate and tetrazolate [2], offer a closely related stereochemistry to carboxylate and, at the same time, a higher basicity, possibly guaranteeing more robust coordinative bonds. Thus, planning to isolate new porous MOFs with long polytopic spacers possessing nitrogen donor sites, we turned our attention to the 1,4-(4-bispyrazolyl)benzene ligand (C12H10N4, H2bpb) [3]. Reacting the deprotonated form of the H2bpb moiety with nickel, copper and zinc salts, we isolated the highly porous homoleptic Ni(bpb) and Zn(bpb) species, and a dense Cu2(bpb) material. Ab-initio powder diffraction methods and thermodiffractometry allowed the determination of their crystal structures and flexibility. The different stereochemical requirements induce, in the 3-D Ni(II) and Zn(II) species, rhombic and square channels respectively, capable of hosting guest molecules and accounting for the 57 and 65% of the total volume. Indeed, both species possess permanent nanoporosity and adsorb large quantities of small gaseous molecules (N2, Ar at 77 K and CO2, CH4 at 273 K), as a consequence of their unusually large surface areas (peaking well above 2000 m2 g-1). The hydrophobic nature of the channels is also adequate for the incorporation of organic vapors (benzene, cyclohexane, 2,2-dimethylbutane) at 298 K, as witnessed by selectivity studies
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
The structural origin of the remarkable performance of the metal–organic framework Fe2(BPEB)3 as ... more The structural origin of the remarkable performance of the metal–organic framework Fe2(BPEB)3 as a CO2 adsorbent (40.5% of the host weight at 298 K and 10 bar) was investigated by combining advanced experimental and computational tools.
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