Inside Cover: Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution (Chem. Eur. J. 49/2017)
International audience; A hydrogen-bonded open framework with pores decorated by pyridyl groups was constructed by off-charge-stoichiometry assembly of protonated tetrakis(4-pyridyloxymethyl)methane and [Al(oxalate)(3)](3-), which are the H-bond donor and acceptor of ionic H-bond interactions, respectively. This supramolecular porous architecture (SPA-2) has 1nm-large pores interconnected in 3D with large solvent-accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good sel…
Self-Assembly of Zr(C2O4)44– Metallotectons and Bisimidazolium Cations: Influence of the Dication on H-Bonded Framework Dimensionality and Material Potential Porosity
Assemblies involving [Zr(C2O4)4]4– metallotectons (C2O42– = oxalate) and linear, flexible, or V-shaped organic cations (H2-Lx)2+ derived from the 1,4-bisimidazol-1-ylbenzene molecule have been envisioned to elaborate porous frameworks based on ionic H-bonds. Five architectures of formula [{(H2-L1)2Zr(C2O4)4}·2H2O] (1), [{(H2-L2)2Zr(C2O4)4}·6H2O] (2), [{(H2-L3)2Zr(C2O4)4}·6H2O] (3), [{(H2-L4)2Zr(C2O4)4}·H2O] (4), and [{(H2-L5)2Zr(C2O4)4}·6H2O] (5) (with L1 = p-bis(imidazol-1-yl)benzene, L2 = p-bis(2-methylimidazol-1-yl)benzene, L3 = p-bis(imidazol-1-yl)-2,5-dimethylbenzene, L4 = p-bis(imidazol-1-ylmethyl)benzene, L5 = m-bis(imidazol-1-yl)benzene) have been obtained; 1–3, and 5 show an open-f…
Efficient growth of sub-micrometric MOF crystals inside the channels of AAO membranes
International audience; A dynamic step-by-step methodology has been implemented to grow the HKUST-1 porous coordination polymer inside commercial anodic aluminium oxide membranes. Efficient crystal growth is achieved from the membrane inner walls and over the whole membrane thickness when copper acetate colloidal suspensions and benzene tricarboxylic acid solutions are forced to flow through the membrane. Sorption properties of the HKUST-1 embedded in membranes show selectivity for CO2 over CO, CH4, O2 and N2 similar to the bulk material.
Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution.
International audience; An hydrogen-bonded open framework with pores decorated by pyridyl groups has been constructed following an off-charge-stoichiometry assemblage of protonated tetrakis(4-pyridyl-oxymethyl)methane and [Al(oxalate)3]3-, respectively the H-bond donor and acceptor of the ionic H-bond interactions. This supramolecular porous architecture (SPA-2) possesses 1 nm-large pores interconnected in 3D with high solvent accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by the means of various carboxylic acids including larger drug molecules. Noteworthy, competing sorption between acetic acid and its halogenated…
Tetradihydrobenzoquinonate and Tetrachloranilate Zr(IV) Complexes: Single-Crystal-to-Single-Crystal Phase Transition and Open-Framework Behavior for K4Zr(DBQ)4.
The molecular complexes K4[Zr(DBQ)4] and K 4[Zr(CA)4], where DBQ2- and CA2- stand respectively for deprotonated dihydroxybenzoquinone and chloranilic acid, are reported. The anionic metal complexes consist of Zr(IV) surrounded by four O,O-chelating ligands. Besides the preparation and crystal structures for the two complexes, we show that in the solid state the DBQ complex forms a 3-D open framework (with 22% accessible volume) that undergoes a crystal-to-crystal phase transition to a compact structure upon guest molecule release. This process is reversible. In the presence of H2O, CO2, and other small molecules, the framework opens and accommodates guest molecules. CO2 adsorption isotherms…
From ZIF-8@Al2O3Composites to Self-Supported ZIF-8 One-Dimensional Superstructures
International audience; Efficient preparation of composite materials consisting of ZIF-8 nanocrystals embedded inside the channels of macroporous anodic aluminum oxide membranes is reported. 1-D self-supported ZIF-8 superstructures are recovered through matrix dissolution.
A robust nanoporous supramolecular metal–organic framework based on ionic hydrogen bonds
International audience; Hydrogen-bond assembly of tripod-like organic cations [H3-MeTrip]3+ (1,2,3-tri(4′-pyridinium-oxyl)-2-methylpropane) and the hexa-anionic complex [Zr2(oxalate)7]6− leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the material at the single-crystal level during a sorption cycle. The framework crystal structure was found to remain the same for the native compound, its activated phase, and after guest resorption. The channels exhibit affinities for polar organic molecules ranging from simple alcohols to aniline. Halogenated molecules and I2 …
Experimental and Theoretical Studies on Magnetic Exchange in Silole-Bridged Diradicals.
International audience; Five bis(tert-butylnitroxide) diradicals connected by a silole [2,5-R2-3,4-diphenylsilole; R = Me3CN(®O.bul.)Z; Z = p-C6H4 (7a), p-C6H4C6H4-p (7b), 1,4-naphthalenediyl (7c), m-C6H4 (7d)] or a thiophene [2,5-R2-thiophene; R = p-Me3CN(®O.bul.)C6H4 (12)] ring as a coupler were studied. Compd. 12 crystallizes in the orthorhombic space group Pna21 with a 20.752(5), b 5.826(5), and c 34.309(5) .ANG.. X-ray crystal structure detn., electronic spectroscopy, variable-temp. EPR spectroscopy, SQUID measurements and DFT computations (UB3LYP/6-31+G*) were used to study the mol. conformations and electronic spin coupling in this series of mols. Whereas compds. 7b, 7c, and 7d are q…
Supramolecular open-framework architectures based on dicarboxylate H-bond acceptors and polytopic cations with three/four N–H+donor units
International audience; Supramolecular assemblages based on anionic H-acceptors and cationic H-donors have been envisioned to elaborate open frameworks maintained by ionic H-bonds. Combinations of di-anionic chloranilate (CA2-), oxalate (Ox2-), or terephthalate (BDC2-) and trisimidazolium or tetrapyridinium derivatives (three and four N-H+ donors, respectively) yielded five architectures of formulae [(H3TrIB)(CA)1.5[middle dot]2DMF[middle dot]2.5H2O] (1), [(H4Tetrapy)(CA)2[middle dot]3DMF] (2), [(H3TrIB)(HOx)(Ox)[middle dot]5H2O] (3), [(H4Tetrapy)(Ox)2[middle dot]5H2O] (4), and [(H4Tetrapy)(BDC)2(H2O)[middle dot]1DMF[middle dot]3H2O] (5) (with TrIB = 1,3,5-trisimidazolylbenzene and Tetrapy …
CCDC 1402188: Experimental Crystal Structure Determination
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CCDC 1537659: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732
CCDC 993985: Experimental Crystal Structure Determination
Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638
CCDC 943452: Experimental Crystal Structure Determination
Related Article: Inhar Imaz, Georges Mouchaham, Nans Roques, Stéphane Brandès, and Jean-Pascal Sutter|2013|Inorg.Chem.|52|11237|doi:10.1021/ic401474f
CCDC 943451: Experimental Crystal Structure Determination
Related Article: Inhar Imaz, Georges Mouchaham, Nans Roques, Stéphane Brandès, and Jean-Pascal Sutter|2013|Inorg.Chem.|52|11237|doi:10.1021/ic401474f
CCDC 993988: Experimental Crystal Structure Determination
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CCDC 993987: Experimental Crystal Structure Determination
Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638
CCDC 1402184: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Marion Gualino, Nans Roques, Carine Duhayon, Stéphane Brandès, Jean-Pascal Sutter|2015|CrystEngComm|17|8906|doi:10.1039/C5CE01070E
CCDC 993983: Experimental Crystal Structure Determination
Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638
CCDC 993984: Experimental Crystal Structure Determination
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CCDC 1537661: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732
CCDC 943453: Experimental Crystal Structure Determination
Related Article: Inhar Imaz, Georges Mouchaham, Nans Roques, Stéphane Brandès, and Jean-Pascal Sutter|2013|Inorg.Chem.|52|11237|doi:10.1021/ic401474f
CCDC 1537660: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732
CCDC 1537663: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732
CCDC 1402187: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Marion Gualino, Nans Roques, Carine Duhayon, Stéphane Brandès, Jean-Pascal Sutter|2015|CrystEngComm|17|8906|doi:10.1039/C5CE01070E
CCDC 993986: Experimental Crystal Structure Determination
Related Article: Nans Roques, Georges Mouchaham, Carine Duhayon, Stéphane Brandès, Aurélie Tachon, Guy Weber, Jean Pierre Bellat, Jean-Pascal Sutter|2014|Chem.-Eur.J.|20|11690|doi:10.1002/chem.201403638
CCDC 1537662: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Nans Roques, Walid Khodja, Carine Duhayon, Yannick Coppel, Stéphane Brandès, Tamás Fodor, Michel Meyer and Jean-Pascal Sutter|2017|Chem.-Eur.J.|23|11818|doi:10.1002/chem.201701732
CCDC 1402186: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Marion Gualino, Nans Roques, Carine Duhayon, Stéphane Brandès, Jean-Pascal Sutter|2015|CrystEngComm|17|8906|doi:10.1039/C5CE01070E
CCDC 1402185: Experimental Crystal Structure Determination
Related Article: Georges Mouchaham, Marion Gualino, Nans Roques, Carine Duhayon, Stéphane Brandès, Jean-Pascal Sutter|2015|CrystEngComm|17|8906|doi:10.1039/C5CE01070E