Crystal Engineering of Metal-Organic Frameworks for Molecular Recognition

A world in which there is a demand for materials with various properties for different needs, requires robust tools to assist in this matter. In this regard, crystal engineering is among the most important tools in materials design and keeps developing in a sustained manner. Obviously, the application of crystal engineering principles to multifunctional microporous materials cannot cause any surprise, and Metal-Organic Frameworks (MOFs), as an example of the latter, stay in focus of scientific and industrial interests.ChemE/Catalysis Engineerin

Crystal structure of 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid dihydrate, C14H16N2O6

C14H16N2O6, triclinic, P1̅ (no. 2), a = 10.0254(5) Å, b = 11.2726(6) Å, c = 13.4494(7) Å, α = 111.535(2)°, β = 92.068(2)°, γ = 102.644(2)°, V = 1368.16(13) Å3, Z = 4, Rgt(F) = 0.047, wRref(F2) = 0.133, T = 150 K.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007–2013) / ERC Grant Agreement No.335746, CrystEngMOF-MMM. S. G.-G. thanks to Ministerio de Economía y Competitividad, MAT2013-40950-R, for financial support.Peer Reviewe

Class-based cape open interface revisited in net framework

A study of a copper-based metal–organic framework (MOF) synthesized by an electrochemical route is presented. Morphological and adsorption properties of the MOF synthesized as bulk powder and on supported copper surfaces were investigated. Differences in these properties and structural refinement studies indicate that when 4,4′,4′′-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB) is used as linker interpenetration can be prevented when the structure is grown on a surface.Graphical abstract: Control of interpenetration of copper-based MOFs on supported surfaces by electrochemical synthesis <br/

Temperature-dependent supramolecular isomerism of lutetium-aminoterephthalate metal-organic frameworks: synthesis, crystallography, and physical properties

Three supramolecular isomers of lutetium metal-organic framework, {Lu2(H2O)4(ATA)3·4H2O}n (Lu-ATA@RT), {Lu2(H2O)2(C3H7NO)2(ATA)3}n (Lu-ATA@100), and {Lu2(C3H7NO)(ATA)3}n (Lu-ATA@150), have been obtained from the reaction of Lu(NO3)3·6H2O with 2-aminoterephthalic acid (ATA) at different temperatures. The resulting structures of Lu-ATA metal-organic frameworks depend on the temperature applied during the synthesis, revealing a temperature-susceptible supramolecular isomerism. Single-crystal X-ray diffraction analyses suggest that new compounds with formula {Lu2(S)x(ATA)3}n (S = solvent: H2O, DMF) display different three-dimensional architectures which consist of dinuclear lutetium building units. The supramolecular isomer Lu-ATA@RT, formed at room temperature, has a pcu-net topology, while its double interpenetrated analogue Lu-ATA@100 assembles at 100 °C under hydrothermal conditions. Hydrothermal synthesis at 150 °C affords formation of the dense Lu-ATA@150 cage-like framework displaying a new hexagonal-packed net topology. All Lu-ATA isomeric phases are porous and display different gas-uptake behavior toward carbon dioxide as a function of polymeric network arrangement. The luminescent properties of Lu-ATA frameworks in the solid state as well as in suspension in the presence of different solvents reveal a solvent-dependent emission.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007−2013)/ERC Grant Agreement n. 335746, CrystEng-MOF-MMM.Peer Reviewe

Crystal structure of 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid dihydrate, C₁₄H₁₆N₂O₆

C14H16N2O6, triclinic, P1 (no. 2), a = 10.0254(5) Å, b = 11.2726(6) Å, c = 13.4494(7) Å, α = 111.535(2)°, β = 92.068(2)°, γ = 102.644(2)°, V = 1368.16(13) Å3, Z = 4, Rgt(F) = 0.047, wRref(F2) = 0.133, T = 150 K.ChemE/Catalysis Engineerin

Temperature-Dependent Supramolecular Isomerism of Lutetium-Aminoterephthalate Metal-Organic Frameworks: Synthesis, Crystallography, and Physical Properties

Three supramolecular isomers of lutetium metal–organic framework, {Lu₂(H₂O)₄(ATA)₃­·4H₂O}_<i>n</i> (<b>Lu-ATA@RT</b>), {Lu₂(H₂O)₂­(C₃H₇NO)₂­(ATA)₃}_<i>n</i> (<b>Lu-ATA@100</b>), and {Lu₂(C₃H₇NO)­(ATA)₃}_<i>n</i> (<b>Lu-ATA@150</b>), have been obtained from the reaction of Lu­(NO₃)₃·6H₂O with 2-aminoterephthalic acid (ATA) at different temperatures. The resulting structures of Lu-ATA metal–organic frameworks depend on the temperature applied during the synthesis, revealing a temperature-susceptible supramolecular isomerism. Single-crystal X-ray diffraction analyses suggest that new compounds with formula {Lu₂(S)_<i>x</i>(ATA)₃}_<i>n</i> (S = solvent: H₂O, DMF) display different three-dimensional architectures which consist of dinuclear lutetium building units. The supramolecular isomer <b>Lu-ATA@RT</b>, formed at room temperature, has a pcu-net topology, while its double interpenetrated analogue <b>Lu-ATA@100</b> assembles at 100 °C under hydrothermal conditions. Hydrothermal synthesis at 150 °C affords formation of the dense <b>Lu-ATA@150</b> cage-like framework displaying a new hexagonal-packed net topology. All Lu-ATA isomeric phases are porous and display different gas-uptake behavior toward carbon dioxide as a function of polymeric network arrangement. The luminescent properties of Lu-ATA frameworks in the solid state as well as in suspension in the presence of different solvents reveal a solvent-dependent emission

Nanosheets of non-layered aluminium metal-organic frameworks through a surfactant-assisted method

European Crystallography Meeting (31st. 2018. Oviedo, Spain

Initial Carbon−Carbon Bond Formation during the Early Stages of Methane Dehydroaromatization

Methane dehydroaromatization (MDA) is among the most challenging processes in catalysis science owing to the inherent harsh reaction conditions and fast catalyst deactivation. To improve this process, understanding the mechanism of the initial C−C bond formation is essential. However, consensus about the actual reaction mechanism is still to be achieved. In this work, using advanced magic-angle spinning (MAS) solid-state NMR spectroscopy, we study in detail the early stages of the reaction over a well-dispersed Mo/H-ZSM-5 catalyst. Simultaneous detection of acetylene (i.e., presumably the direct C−C bond-forming product from methane), methylidene, allenes, acetal, and surface-formate species, along with the typical olefinic/aromatic species, allow us to conclude the existence of at least two independent C−H activation pathways. Moreover, this study emphasizes the significance of mobility-dependent host–guest chemistry between an inorganic zeolite and its trapped organic species during heterogeneous catalysis

Initial Carbon−Carbon Bond Formation during the Early Stages of Methane Dehydroaromatization

Methane dehydroaromatization (MDA) is among the most challenging processes in catalysis science owing to the inherent harsh reaction conditions and fast catalyst deactivation. To improve this process, understanding the mechanism of the initial C−C bond formation is essential. However, consensus about the actual reaction mechanism is still to be achieved. In this work, using advanced magic-angle spinning (MAS) solid-state NMR spectroscopy, we study in detail the early stages of the reaction over a well-dispersed Mo/H-ZSM-5 catalyst. Simultaneous detection of acetylene (i.e., presumably the direct C−C bond-forming product from methane), methylidene, allenes, acetal, and surface-formate species, along with the typical olefinic/aromatic species, allow us to conclude the existence of at least two independent C−H activation pathways. Moreover, this study emphasizes the significance of mobility-dependent host–guest chemistry between an inorganic zeolite and its trapped organic species during heterogeneous catalysis

Initial Carbon−Carbon Bond Formation during the Early Stages of Methane Dehydroaromatization

Methane dehydroaromatization (MDA) is among the most challenging processes in catalysis science owing to the inherent harsh reaction conditions and fast catalyst deactivation. To improve this process, understanding the mechanism of the initial C−C bond formation is essential. However, consensus about the actual reaction mechanism is still to be achieved. In this work, using advanced magic-angle spinning (MAS) solid-state NMR spectroscopy, we study in detail the early stages of the reaction over a well-dispersed Mo/H-ZSM-5 catalyst. Simultaneous detection of acetylene (i.e., presumably the direct C−C bond-forming product from methane), methylidene, allenes, acetal, and surface-formate species, along with the typical olefinic/aromatic species, allow us to conclude the existence of at least two independent C−H activation pathways. Moreover, this study emphasizes the significance of mobility-dependent host–guest chemistry between an inorganic zeolite and its trapped organic species during heterogeneous catalysis