Highly Porous Scandium(III) Tetrafluoroisophthalate Framework for Adsorptive Separation of Light Alkanes.

The separation of light alkanes is one of the most important tasks for modern industry due to the widespread use of ethane and propane as chemical feedstocks. Their extraction from natural gas is a challenging task and is now carried out by cryogenic distillation at a limited number of plants around the world. The development of new materials for adsorption separation is therefore important.

Metal-organic frameworks with a sulfur-rich heterocycle: synthesis, gas adsorption properties, and metal exchange.

Three new three-dimensional (3D) metal-organic frameworks [M(ttdc)(dabco)] (M = Zn(II), 1-Zn; Cu(II), 1-Cu; and Zn/Cu, 1-ZnCu) based on thieno[3,2-]thiophene-2,5-dicarboxylate (ttdc) were synthesized and characterized by a combination of physicochemical methods (single crystal X-ray diffraction, powder X-ray diffraction, chemical and thermogravimetric analyses and IR spectroscopy). 1-Cu demonstrated permanent porosity ( = 0.790 cm g and = 1725 m g) and significant CO, CH, CH, CH and CH gas uptakes under ambient conditions.

Low field mobility in bulk GaN and its ternary AlGaN/GaN compounds (quantum kinetic approach).

Analytical expressions for the low-field mobility of charge carrier gases with three-(3D), two-(2D) and one-(1D) dimensionalities are obtained. Multi-ion ionized impurities scattering, acoustic and polar optic phonons are considered as scattering mechanisms. The calculated values of mobility are compared to known experimental data for bulk (3D) n-and p-type wurtzite, n-type zinc-blende GaN crystals and low dimensional (2D and 1D) ternary GaAlN compounds.

Series of Cadmium-Organic Frameworks Based on Mixed Flexible and Rigid Ligands: Single-Crystal-to-Single-Crystal Transformations, Sorption, and Luminescence Properties.

Here, we present a series of Cd(II) coordination polymers containing two types of ligands: sterically rigid terephthalate derivatives (bdc-NO and bdc-Br) and flexible bis(2-methylimidazolyl)propane (bmip). The combination of two types of ligands is used to obtain and characterize compounds by single crystal and powder X-ray diffraction, FT-IR, elemental analysis, and TGA. Guest exchange results in structural transformations.

Bulk plasmon-limited mobility in semiconductors: from bulk to nanowires.

Analytical expressions are obtained for the low-field mobility in semiconductors for scattering of three-dimensional (3D), two-dimensional (2D), and one-dimensional (1D) charged carriers by bulk plasmons. The consideration is based on the quantum kinetic equation and model distribution function in form of a shifted Fermi distribution and includes calculations of the dielectric function of 3D, 2D and 1D carriers in the random phase approximation. The resulting analytical expressions give dependences of the plasmon limited mobility on the dimensionality of charge carrier system, their density, effective mass, temperature and confining dimensions.

Metal-mediated tunability of MOF-based optical modulators.

We report on the design of 1D MOFs based on a nopinane-annelated organic ligand and Co(II) or Ni(II), the variation of which allows tuning the optical modulation bandwidth. Structural and time-resolved analysis revealed the optical modulation mechanism, the rates and its endurance, thereby enriching the list of sustainable MOFs for tunable optical modulators.

An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions.

Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(II) with -tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported.

A Series of Metal-Organic Frameworks with 2,2'-Bipyridyl Derivatives: Synthesis vs. Structure Relationships, Adsorption, and Magnetic Studies.

Five new metal-organic frameworks based on Mn(II) and 2,2'-bithiophen-5,5'-dicarboxylate (btdc) with various chelating N-donor ligands (2,2'-bipyridyl = bpy; 5,5'-dimethyl-2,2'-bipyridyl = 5,5'-dmbpy; 4,4'-dimethyl-2,2'-bipyridyl = 4,4'-dmbpy) [Mn(btdc)(bpy)]·4DMF, ; [Mn(btdc)(5,5'-dmbpy)]·5DMF, ; [Mn(btdc)(4,4;-dmbpy)], ; [Mn(btdc)(bpy)(dmf)]·0.5DMF, ; [Mn(btdc)(5,5'-dmbpy)(dmf)]·DMF, (dmf, DMF = N,N-dimethylformamide) have been synthesized, and their crystal structure has been established using single-crystal X-ray diffraction analysis (XRD). The chemical and phase purities of Compounds - have been confirmed via powder X-ray diffraction, thermogravimetric, and chemical analyses as well as IR spectroscopy.

Enhanced Adsorption Selectivity of Carbon Dioxide and Ethane on Porous Metal-Organic Framework Functionalized by a Sulfur-Rich Heterocycle.

Porous metal-organic framework [Zn(ttdc)(bpy)] () based on thieno [3,2-b]thiophenedicarboxylate (ttdc) was synthesized and characterized. The structure contains intersected zig-zag channels with an average aperture of 4 × 6 Å and a 49% () guest-accessible pore volume. Gas adsorption studies confirmed the microporous nature of with a specific surface area (BET model) of 952 m·g and a pore volume of 0.

New Type of Nanocomposite CsHPO-UiO-66 Electrolyte with High Proton Conductivity.

New (1−x)CsH2PO4−xUiO-66 electrolytes with high proton conductivity and thermal stability at 230−250 °C were developed. The phase composition and proton conductivity of nanocomposites (x = 0−0.15) were investigated in detail.

Selective gas adsorption by calixarene-based porous octahedral M coordination cages.

Giant octahedral M coordination cages were prepared self-assembly of sulfonylcalix[4]arene-supported tetranuclear M(II) clusters (M = Co, Ni) with hybrid linker based on tris(dipyrrinato)cobalt(III) complexes appended with peripherical carboxylic groups. Due to intrinsic and extrinsic porosity, the obtained solid-state supramolecular architectures demonstrated good performance as adsorbents for the separation of industrially important gases mixtures.

Structural Diversity and Carbon Dioxide Sorption Selectivity of Zinc(II) Metal-Organic Frameworks Based on Bis(1,2,4-triazol-1-yl)methane and Terephthalic Acid.

A three-component reaction between the 1,4-benzenedicarboxylic (terephthalic) acid (Hbdc), bis(1,2,4-triazol-1-yl)methane (btrm) and zinc nitrate was studied, and three new coordination polymers were isolated by a careful selection of the reaction conditions. Coordination polymers {[Zn(DMF)(btrm)(bdc)]·nDMF} and {[Zn(btrm)(bdc)]·nDMF} containing trinuclear {Zn(bdc)} secondary building units are joined by btrm auxiliary linkers into three-dimensional metal-organic frameworks. The coordination polymer {[Zn(bdc)(btrm)]∙nDMF} consists of Zn cations joined by bdc and btrm linkers into a two-fold interpenetrated network.

Effect of Pore Filling on Properties of Nanocomposites LiClO-MIL-101(Cr) with High Ionic Conductivity.

Experimental data on nitrogen adsorption, pellets density and ionic conductivity of nanocomposite solid electrolytes (1−x)LiClO4−xMIL-101(Cr) were interpreted in frames of the model of the composite in which the lithium salt fills the pores of a metal-organic framework MIL-101(Cr). According to the model, the concentration of lithium salt located in the pores reaches a maximum at the concentration x = xmax which is defined by a ratio of the molar volume of LiClO4 and the total volume of accessible pores in the MIL-101(Cr) framework. The model allows one to describe the dependences of pore volume and pellet density on the concentration of MIL-101(Cr).

Self-Assembled Microporous M-HOFs Based on an Octahedral Rhenium Cluster with Benzimidazole.

Substitution of apical halide ligands in [{ReSe}X] (X = Cl, Br) by benzimidazole (bimzH) accompanied by a self-assembly process leads to the formation of microporous Re-based hydrogen-bonded organic frameworks (Re-HOFs) constructed on N-H···X hydrogen bonds and π-π-stacking interactions between bimzH ligands. Re-HOFs demonstrate sorption properties with a Brunauer-Emmett-Teller surface area of up to 443 m g and luminescence with a quantum yield and an emission lifetime of up to 0.16 and 16 μs, respectively.

Metal-organic framework application for mercury speciation using solid phase extraction followed by direct thermal release-electrothermal atomization atomic absorption spectrophotometric detection (ETA AAS).

Metal-organic frameworks (MOFs) are increasingly used in analytical chemistry for pre-concentration of trace elements followed by their determination using modern analytical techniques. However, there are a limited number of publications concerning the use of MOFs for speciation purposes, while their structural and functional features are perspective for the element species selective extraction and pre-concentration. It is known that mercury refers to the most hazardous elements which species demonstrate different toxicity, migration routes and bioavailability as well.

Heteroleptic La Anilate/Dicarboxylate Based Neutral 3D-Coordination Polymers.

Three new 3D metal-organic frameworks of lanthanum based on mixed anionic ligands, [(La(pQ)(BDC))·4DMF], [(La(pQ)(DHBDC))·4DMF], [(La(CA)(BDC))·4DMF] (pQ-dianion of 2,5-dihydroxy-3,6-di-tert-butyl-para-quinone, CA-dianion of chloranilic acid, BDC-1,4-benzenedicarboxylate, DHBDC-2,5-dihydroxy-1,4-benzenedicarboxylate and DMF-N,N'-dimethylformamide), were synthesized using solvothermal methodology. Coordination polymers demonstrate the rare or topology of a 3D framework. The homoleptic 2D-coordination polymer [(La(pQ))·4DMF] was obtained as a by-product in the course of synthetic procedure optimization.

Proton conductivity as a function of the metal center in porphyrinylphosphonate-based MOFs.

The rational design of metal-organic frameworks (MOFs) is highly important for the development of new proton conductors. Porphyrinylphosphonate-based MOFs, providing the directed tuning of physical and chemical properties of materials through the modification of a macrocycle, are potentially high-conducting systems. In this work the synthesis and characterization of novel anionic Zn-containing MOF based on palladium(ii) meso-tetrakis(3-(phosphonatophenyl))porphyrinate, IPCE-2Pd, are reported.

Metal-Organic Frameworks for Highly Selective Separation of Xylene Isomers and Single-Crystal X-ray Study of Aromatic Guest-Host Inclusion Compounds.

Separation of hydrocarbon molecules, such as benzene/cyclohexane and -xylene/-xylene/-xylene, is relevant due to their widespread application as chemical feedstock but challenging because of their similar boiling points and close molecular sizes. Physisorption separation could offer an energy-efficient solution to this problem, but the design and synthesis of sorbents that exhibit high selectivity for one of the hydrocarbons remain a largely unmet challenge. Herein, we report a new heterometallic MOF with a unique tortuous shape of channels decorated with aromatic sorption sites [LiZn(bpy)(ndc)] (, bpy = 4,4'-bipyridine, ndc = naphthalene-1,4-dicarboxylate) and study of its benzene/cyclohexane and xylene vapor and liquid separation.

3D Metal-Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis, Crystal Structures, Gas Adsorption, and Magnetic Properties.

Three new 3D metal-organic porous frameworks based on Co(II) and 2,2'-bithiophen-5,5'-dicarboxylate (btdc) [Co(btdc)(bpy)]·4DMF, ; [Co(btdc)(pz)(dmf)]·4DMF·1.5HO, ; [Co(btdc)(dmf)]∙2DMF∙2HO, (bpy = 2,2'-bipyridyl, pz = pyrazine, dmf = ,-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co(RCOO)}, connected either by btdc ligands (, ) or by both btdc and pz bridging ligands ().

Isomeric Scandium-Organic Frameworks with High Hydrolytic Stability and Selective Adsorption of Acetylene.

Two solvent-controlled topological isomers of scandium-organic frameworks [Sc(Hpzc)(pzc)]·DMF·2HO (·DMF·2HO) and [Sc(Hpzc)(pzc)]·DMA·4HO (·DMA·4HO) were synthesized using 2,5-pyrazinedicarboxylate (pzc) (DMF = dimethylformamide; DMA = dimethylacetamide). Despite the isomeric nature of the obtained metal-organic frameworks (MOFs), they possess different structural features and unique adsorption properties toward gases and iodine. The compound has widely spread among MOF structures a topology with ultranarrow channels, which together with inner surface functionalization leads to enhanced CO adsorption and high selectivity factors in CO/CH and CO/N gas mixtures (25.

Heterometallic MOFs constructed from thiophene and furandicarboxylate ligands for heavy metal luminescence sensing.

Rational design of a series of new heterometallic MOFs was carried out by the judicious choice of the corresponding synthesis conditions and ligand geometry. Three heterometallic MOFs (H2NMe2)[LiZn(dmf)(tdc)2]·DMF·H2O (1), [{LiZn}2Li2Zn2(dmf)6(tdc)6]·6DMF·H2O (2) and [Li2Zn2(dmf)2(fdc)3]·2DMF·2H2O (3) were obtained on the basis of the pre-synthesized pivalate complex [Li2Zn2(py)2(piv)6]. The angle between carboxylic groups greatly affects the possibility of retaining the initial tetranuclear node in the structure of the obtained MOFs.

Hydrothermal Activation of Porous Nitrogen-Doped Carbon Materials for Electrochemical Capacitors and Sodium-Ion Batteries.

Highly porous nitrogen-doped carbon nanomaterials have distinct advantages in energy storage and conversion technologies. In the present work, hydrothermal treatments in water or ammonia solution were used for modification of mesoporous nitrogen-doped graphitic carbon, synthesized by deposition of acetonitrile vapors on the pyrolysis products of calcium tartrate. Morphology, composition, and textural characteristics of the original and activated materials were studied by transmission electron microscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, infrared spectroscopy, and nitrogen gas adsorption method.

Structural Dynamics and Adsorption Properties of the Breathing Microporous Aliphatic Metal-Organic Framework.

A mixed-ligand metal-organic framework [Zn(chdc)(dabco)]·2NMP (chdc = -1,4-cyclohexanedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane; NMP = -methylpyrrolidone) was synthesized under solvothermal conditions.