Regioselective, Stereoselective, and Conformationally Controlled Synthesis of (η⁴-Tetraarylcyclobutadiene)(η⁵-carbomethoxycyclopentadienyl)cobalt Metallocenes

The Friedel–Crafts reaction of (η⁴-tetraphenylcyclobutadiene)(η⁵-carbomethoxycyclopentadienyl)cobalt with acid chlorides/aluminum chloride resulted exclusively in <i>para</i>-phenyl acylation. Both monoacylated (1.1 equiv of RCOCl/AlCl₃) and tetraacylated products (>4 equiv of RCOCl/AlCl₃) were synthesized. Reaction of PhCC(<i>o</i>-RC₆H₄) (R = Me, <i>i</i>-Pr) with Na(C₅H₄CO₂Me) and CoCl(PPh₃)₃ gave predominantly (η⁴-1,3-diaryl-2,4-diphenylcyclobutadiene)(η⁵-carbomethoxycyclopentadienyl)cobalt metallocenes (1,3-[<i>trans</i>] vs 1,2-[<i>cis</i>] selectivity up to 6:1). Conformational control of Friedel–Crafts reactions on the major isomers gave exclusively <i>para</i>-acylation of the unsubstituted phenyl groups

Structural Variability in Multifunctional Metal Xylenediaminetetraphosphonate Hybrids

Two new families of divalent metal hybrid derivatives from the aromatic tetraphosphonic acids 1,4- and 1,3-<i>bis</i>(aminomethyl)­benzene-<i>N</i>,<i>N</i>′-<i>bis</i>(methylenephosphonic acid), (H₂O₃PCH₂)₂–N–CH₂C₆H₄CH₂–N­(CH₂PO₃H₂)₂ (designated herein as <b><i>p</i>-H₈L</b> and <b><i>m</i>-H₈L</b>) have been synthesized by crystallization at room temperature and hydrothermal conditions. The crystal structures of M­[(HO₃PCH₂)₂N­(H)­CH₂C₆H₄CH₂N­(H)­(CH₂PO₃H)₂(H₂O)₂]·2H₂O (M = Mg, Co, and Zn), <b>M–(<i>p</i>-H₆L)</b>, and M­[(HO₃PCH₂)₂N­(H)­CH₂C₆H₄CH₂N­(H)­(CH₂PO₃H)₂]·<i>n</i>H₂O (M = Ca, Mg, Co, and Zn and <i>n</i> = 1–1.5), <b><b>M–(<i>m</i>-H₆L)</b></b>, were solved ab initio by synchrotron powder diffraction data using the direct methods and subsequently refined using the Rietveld method. The crystal structure of the isostructural <b><b>M–(<i>p</i>-H₆L)</b></b> is constituted by organic–inorganic monodimensional chains where the phosphonate moiety acts as a bidentate chelating ligand bridging two metal octahedra. <b><b>M–(<i>m</i>-H₆L)</b></b> compounds exhibit a 3D pillared open-framework with small 1D channels filled with water molecules. These channels are formed by the pillaring action of the organic ligand connecting adjacent layers through the phosphonate oxygens. Thermogravimetric and X-ray thermodiffraction analyses of <b><b>M–(<i>p</i>-H₆L)</b></b> showed that the integrity of their crystalline structures is maintained up to 470 K, without significant reduction of water content, while thermal decomposition takes place above 580 K. The utility of <b><b>M–(<i>p</i>-H₆L)</b></b> (M = Mg and Zn) hybrid materials in corrosion protection was investigated in acidic aqueous solutions. In addition, the impedance data indicate both families of compounds display similar proton conductivities (σ ∼ 9.4 × 10^–5 S·cm^–1, at 98% RH and 297 K), although different proton transfer mechanisms are involved

Structural Variability in Multifunctional Metal Xylenediaminetetraphosphonate Hybrids

Two new families of divalent metal hybrid derivatives from the aromatic tetraphosphonic acids 1,4- and 1,3-<i>bis</i>(aminomethyl)­benzene-<i>N</i>,<i>N</i>′-<i>bis</i>(methylenephosphonic acid), (H₂O₃PCH₂)₂–N–CH₂C₆H₄CH₂–N­(CH₂PO₃H₂)₂ (designated herein as <b><i>p</i>-H₈L</b> and <b><i>m</i>-H₈L</b>) have been synthesized by crystallization at room temperature and hydrothermal conditions. The crystal structures of M­[(HO₃PCH₂)₂N­(H)­CH₂C₆H₄CH₂N­(H)­(CH₂PO₃H)₂(H₂O)₂]·2H₂O (M = Mg, Co, and Zn), <b>M–(<i>p</i>-H₆L)</b>, and M­[(HO₃PCH₂)₂N­(H)­CH₂C₆H₄CH₂N­(H)­(CH₂PO₃H)₂]·<i>n</i>H₂O (M = Ca, Mg, Co, and Zn and <i>n</i> = 1–1.5), <b><b>M–(<i>m</i>-H₆L)</b></b>, were solved ab initio by synchrotron powder diffraction data using the direct methods and subsequently refined using the Rietveld method. The crystal structure of the isostructural <b><b>M–(<i>p</i>-H₆L)</b></b> is constituted by organic–inorganic monodimensional chains where the phosphonate moiety acts as a bidentate chelating ligand bridging two metal octahedra. <b><b>M–(<i>m</i>-H₆L)</b></b> compounds exhibit a 3D pillared open-framework with small 1D channels filled with water molecules. These channels are formed by the pillaring action of the organic ligand connecting adjacent layers through the phosphonate oxygens. Thermogravimetric and X-ray thermodiffraction analyses of <b><b>M–(<i>p</i>-H₆L)</b></b> showed that the integrity of their crystalline structures is maintained up to 470 K, without significant reduction of water content, while thermal decomposition takes place above 580 K. The utility of <b><b>M–(<i>p</i>-H₆L)</b></b> (M = Mg and Zn) hybrid materials in corrosion protection was investigated in acidic aqueous solutions. In addition, the impedance data indicate both families of compounds display similar proton conductivities (σ ∼ 9.4 × 10^–5 S·cm^–1, at 98% RH and 297 K), although different proton transfer mechanisms are involved

High Proton Conductivity in a Flexible, Cross-Linked, Ultramicroporous Magnesium Tetraphosphonate Hybrid Framework

Multifunctional materials, especially those combining two or more properties of interest, are attracting immense attention due to their potential applications. MOFs, metal organic frameworks, can be regarded as multifunctional materials if they show another useful property in addition to the adsorption behavior. Here, we report a new multifunctional light hybrid, MgH₆ODTMP·2H₂O­(DMF)_0.5 (<b>1</b>), which has been synthesized using the tetraphosphonic acid H₈ODTMP, octamethylenediamine-<i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetrakis­(methylenephosphonic acid), by high-throughput methodology. Its crystal structure, solved by Patterson-function direct methods from synchrotron powder X-ray diffraction, was characterized by a 3D pillared open framework containing cross-linked 1D channels filled with water and DMF. Upon H₂O and DMF removal and subsequent rehydration, MgH₆ODTMP·2H₂O (<b>2</b>) and MgH₆ODTMP·6H₂O (<b>3</b>) can be formed. These processes take place through crystalline–quasi-amorphous–crystalline transformations, during which the integrity of the framework is maintained. A water adsorption study, at constant temperature, showed that this magnesium tetraphosphonate hybrid reversibly equilibrates its lattice water content as a function of the water partial pressure. Combination of the structural study and gas adsorption characterization (N₂, CO₂, and CH₄) indicates an ultramicroporous framework. High-pressure CO₂ adsorption data are also reported. Finally, impedance data indicates that <b>3</b> has high proton conductivity σ = 1.6 × 10^–3 S cm^–1 at <i>T</i> = 292 K at ∼100% relative humidity with an activation energy of 0.31 eV

High Proton Conductivity in a Flexible, Cross-Linked, Ultramicroporous Magnesium Tetraphosphonate Hybrid Framework

Multifunctional materials, especially those combining two or more properties of interest, are attracting immense attention due to their potential applications. MOFs, metal organic frameworks, can be regarded as multifunctional materials if they show another useful property in addition to the adsorption behavior. Here, we report a new multifunctional light hybrid, MgH₆ODTMP·2H₂O­(DMF)_0.5 (<b>1</b>), which has been synthesized using the tetraphosphonic acid H₈ODTMP, octamethylenediamine-<i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetrakis­(methylenephosphonic acid), by high-throughput methodology. Its crystal structure, solved by Patterson-function direct methods from synchrotron powder X-ray diffraction, was characterized by a 3D pillared open framework containing cross-linked 1D channels filled with water and DMF. Upon H₂O and DMF removal and subsequent rehydration, MgH₆ODTMP·2H₂O (<b>2</b>) and MgH₆ODTMP·6H₂O (<b>3</b>) can be formed. These processes take place through crystalline–quasi-amorphous–crystalline transformations, during which the integrity of the framework is maintained. A water adsorption study, at constant temperature, showed that this magnesium tetraphosphonate hybrid reversibly equilibrates its lattice water content as a function of the water partial pressure. Combination of the structural study and gas adsorption characterization (N₂, CO₂, and CH₄) indicates an ultramicroporous framework. High-pressure CO₂ adsorption data are also reported. Finally, impedance data indicates that <b>3</b> has high proton conductivity σ = 1.6 × 10^–3 S cm^–1 at <i>T</i> = 292 K at ∼100% relative humidity with an activation energy of 0.31 eV