Résumés Année 2017
"Exceptional selectivity, hysteresis and activation-dependent breathing adsorption of a Zn metal-organic framework"
E. R. ENGEL, A. JOUAITI, C. X. BEZUIDENHOUT, M. W. HOSSEINI, L. J. BARBOUR, Angewandte Chemie, 2017, 56, 8874-8878.
Abstract: A non-interpenetrated Zn MOF with paddle-wheel SBU has been activated by direct thermal evacuation, via guest exchange with a volatile solvent, and by supercritical drying. The product of standard thermal evacuation is a mixture of crystalline phases and amorphous content. Exchange with a volatile solvent prior to activation produces a pure breathing phase with high sorption capacity, selectivity for CO2 over N2 and CH4, and extremely broad hysteresis. Supercritical drying can be used to access a guest-free open phase. Furthermore, for the breathing phase we have used pressure-resolved DSC to investigate the systematic loss of sorption capacity with increasing cycles of sorption and desorption, an important factor to be considered in the application of flexible MOFs for gas storage and separation.
"Molecular tectonics : from a binuclear metallamacrocycle to a 1D isostructural coordination networks based on tetracyanomethyl[1.1.1.1]metacyclophane and silver cation"
E. CHERNOVA, A. S. OVSYANNIKOV,S. FERLAY, S. E. SOLOVIEVA,I. S. ANTIPIN, KONOVALOV, N. KYRITSAKAn, M. W. HOSSEINI, Mendeleev Communications., 2017, 27, 260 - 262.
Abstract: Depending on the nature of the anion (NO3- or BF4-) and stoichiometry, combinations, under self-assembly conditions, of the [1.1.1.1]metacyclophane 2 adopting a bloked 1,3-alternate conformation and bearing four cyanomethylene groups, with silver cations, lead either to the formation of a 1D coordination network or a discrete binuclear metallomacrocycle.
"AzaBODIPY based coordination polymers"
A. MAZEL, S. BAUDEON, M. W. HOSSEINI, CrystEngComm., 2017, 19, 897–900.
Abstract: Two azaBODIPY derivatives bearing two divergently oriented benzonitrile groups at the distal positions have been used as tectons for the construction of coordination polymers, upon assembly with Ag(I) salts.
"Molecular tectonics: hierarchical organization of heterobimetallic coordination networks into heterotrimetallic core-shell crystals"
F. ZHANG, C. R. R. ADOLF, N. ZIGON, S. FERLAY, N. KYRITSAKA, M. W. HOSSEINI, Chem. Commun., 2017, 53, 3587-3590.
Abstract: Combinations of a neutral Pt(II) organometallic tecton bearing two triphenylphosphine and two 3-ethynylpyridyl coordinating moieties in trans positions with MX2 complexes (M = Co(II) and X = Cl- or Br- and M = Zn(II) and X = Cl-) lead to the formation of isostructural 1D heterobimetallic coordination compounds. By 3D epitaxial growth processes, using coordination bonding, heterotrimetallic core-shell crystals are generated by growth of crystalline layers on seed crystals.
"Molecular tectonics: Manganese (II), Copper(II) and Zinc(II) 1D coordination polymers based on tetramercaptothiacalix[4]arene bearing benzoate coordinating groups"
A. S. OVSYANNIKOV,S. FERLAY, S. E. SOLOVIEVA,I. S. ANTIPIN, A. I. KONOVALOV, N. KYRITSAKAS, M. W. HOSSEINI, Macroheterocycles, 2017, 10, 147-153.
Abstract: The combinations under mild conditions of the carboxylic appended tetramercaptotetrathiacalix[4]arene (TMTCA) derivative 2 blocked in 1,3-A conformation with acetate salts of octahedral Copper(II), Manganese(II) and Zinc(II) and pyridine, leads to the formation, in the crystalline state, of new coordination 1D networks. Whereas for Copper(II) and Manganese(II), 1D linear coordination polymers are observed, for Zinc(II), a zigzag chain has been evidenced.
"Molecular tectonics: gas adsorption and chiral uptake of (L)- and (D)- tryptophan by homochiral porous coordination polymers"
D. ASNAGHI, R. CORSO, P. LARPENT,I. BASSANETTI, A. JOUAITI, N. KYRITSAKAS, A. COMOTTI, P. SOZZANI, M. W. HOSSEINI, Chem. Commun., 2017, 53, 5740-5743.
Abstract: Combinations of two enantiomerically pure organic tectons 1 and 3 with either Zn(II) or Cu(II) cations lead to the formation of four homochiral 3D networks among which two, 1-Cu and 3-Cu, are robust porous crystals displaying homochiral cavities and permanent microporosity. 3-Cu porous crystals capture 66% and 20% of L- and D-tryptophan, respectively, after 30 min adsorption.
"Formation of binuclear neutral Copper(II) complexes based on p-tert-butyl- calix[4]arene and thiacalix[4]arene in 1,3-A conformation bearing four catechol at their lower rim"
M. H. NOAMANE, S. FERLAY, R. ABIDI, N. KYRITSAKAS, M. W. HOSSEINI, Inorganica Chimica Acta., 2017, dx.doi.org/10.1016/j.ica.2017.04.047.
Abstract: Two new multivalent ligands 1 and 2, based on calix[4]arene and thiacalix[4]arene backbones in 1,3-Alternate conformation, bearing four iminocatechol coordinating units have been prepared and structurally characterized both in solution and in the crystalline phase. Combinations of compounds 1 and 2 with Cu(II) afford neutral binuclear complexes 1-Cu2 and 2-Cu2, characterized in the solid state. In both cases, the metal centre, surrounded by a O3N set of heteroatoms, adopts a deformed square planar coordination geometry. In solution, the propensity of ligands 1 and 2 to bind M2+ cations ((M = Co, Ni, Cu and Zn) was also demonstrated. In 1/1 MeOH/CHCl3 mixture and at room temperature, the following stability sequence Ni2+< Zn2+ < Co2+ << Cu2+ was observed for both binuclear 1-M2 and 2-M2 complexes.
"Discrete binuclear and tetranuclear silver complexes based on ortho-imino- or ortho-amino-pyridyl appended p-tert-butyl-calix[4]arene or p-tert-butyl-thiacalix[4]arene in 1,3-alternate conformation"
M. H. NOAMANE, S. FERLAY, R. ABIDI, N. KYRITSAKAS, M. W. HOSSEINI, Eur.JIC., 2017, 27, 3327–3336.
Abstract: The four new multivalent ligands 5-8 derived from calix[4]arene and thiacalix[4]arene backbones in 1,3-Alternate conformation bearing ortho-imino- and ortho-amino-methylpyridine chelating sites have been designed, prepared and characterized. Owing to the imposed 1,3-Alternate conformation of the backbone, ligands 5-8 offer two coordinating pockets composed of two sets of chelates located above and below the mean place of the macrocyclic framework. Ligands 6-8, independent of the nature of the anion associated with Ag+ cation, form binuclear silver complexes (AgX, X = BF4-, PF6-, SbF6-, AsF6-, NO3-) in solution and in the solid state. Ligand 7, in the presence of an excess of Ag+, also forms tetranuclear silver complexes 7-(AgBF4)4, and 7-(AgNO3)4 in presence of two different auxiliary ligands (H2O or NO3-) that have been characterized in the solid state. Due to a rather short Ag-Ag distance of ca 2.89 Å, the tetranuclear complex 7-(AgBF4)4 is emissive in the solid state, at 298 K (exc = 295 nm, em = 425 nm) resulting from argentophilic interactions between the closely positioned silver cations.
"Synthesis of multivalent oxamate ligands based on calix[4]arene and thiacalix[4]arene backbones in 1,3-Alternate conformation"
M. H. NOAMANE, S. FERLAY, R. ABIDI, M. W. HOSSEINI, Tetrahedron., 2017, 73, 4259-4264.
Abstract: Five new multivalent ligands based on either p-tert-butythiacalix[4]arene (TCA) 1 or p-tert-butylcalix[4]arene (CA) 2 backbones in 1,3-Alternate conformation bearing four oxamate coordinating groups at their lower rim were designed and synthesized by a multistep strategy. These ligands differ either by the nature of the calix[4]arene backbone (CA or TCA) or by the nature of the spacer ((CH2)n) connecting the oxamate binding units to the backbone.
"Solvent and anion effects on the organization of a luminescent [2+2] BODIPY/Ag(I) metallamacrocycle in the crystalline state"
F. ZHANG, S. BAUDRON, M. W. HOSSEINI, CrystEngComm 2017, 19, 4393-4400.
"Synthesis of para- and meta-imino- or -amino-methyl pyridyl appended p-tert-butyl-calix[4]arene or p-tert-butyl-thiacalix[4]arene in 1,3-Alternate conformation"
M. H. NOAMANE, S. FERLAY, R. ABIDI, N. KYRITSAKAS, M. W. HOSSEINI, New J. Chem., 2017, 41, 6334-6339.
Abstract: The multistep synthesis of eight new ligands based on either calix[4]arene or thiacalix[4]arene backbone blocked in 1,3-Alternate conformation was achieved. Both types of backbones were functionalized with pyridyl coordinating units using either imino or amino junctions. The introduction of the pyridyl units was achieved using either the position 3 (meta) or 4 (para) of the aromatic moiety. Four out of the eight ligands have been structurally investigated in the solid state by X-ray diffraction methods on single crystals.
"Tuning photochemical properties of phosphorus(V) porphyrins photosensitizers"
I. N. MESHKOV, V. BULACH, Y. G. GORBUNOV, F. E. GOSTEV, V. A. NADTOCHENKO, A. Y. TSIVADZE, M. W. HOSSEINI, Chem. Comm., 2017, DOI: 10.1039/C7CC06052A.
Abstract: Photosensitizing and emission properties of P(V) porphyrins were studied. The nature of the axial ligands, occupying the apical position on P centre adopting an octahedral coordination geometry, strongly influences singlet oxygen generation and charge transfer and allows to switch between the two processes.
