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.

Solvatomorphic phase transitions and tunable luminescence emission in lanthanide metal-organic frameworks.

Four new metal-organic frameworks with the formulae [Sm(phen)(NO)(chdc)]·2solv, where solv = ,-dimethylformamide (DMF; 1), ,-dimethylacetamide (DMA; 2), ,-diethylformamide (DEF; 3), -formylpiperidine (NFP; 4), phen = 1,10-phenanthroline and chdc = -1,4-cyclohexanedicarboxylate were synthesized and structurally characterized. These compounds are based on similar binuclear samarium(III)-carboxylate blocks, bound by flexible chdc linkers into layered -type coordination networks. The amide solvents drive different intralayer block orientations between 1 and 2-4 and different layer-to-layer packings in all the described compounds.

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.

Ln-MOF-Based Hydrogel Films with Tunable Luminescence and Afterglow Behavior for Visual Detection of Ofloxacin and Anti-Counterfeiting Applications.

Highly selective and sensitive quantitative detection of ofloxacin (OFX) at ultralow concentrations in aqueous media and development of new afterglow materials remains a challenge. Herein, a new 2D water-stable lanthanide metal-organic framework (NIIC-2-Tb) is proposed, which exhibits high selectivity towards OFX through the luminescence quenching with the lowest detection limit (1.1 × 10 M) reported to date and a fast response within 6 s.

An electrochemical sensor based on carbon composites derived from bisbenzimidazole biphenyl coordination polymers for dihydroxybenzene isomers detection.

Co-based coordination polymers (CoCP) based on 4,4'-bis(1H-benzo[d]imidazol-1-yl)-1,1'-biphenyl (BMB) ligand have been synthesized for the first time by the solvothermal method. The CoCP was carbonized at 700 °C under a nitrogen atmosphere to obtain carbide coordination polymer (C-CoCP) with a unique two-dimensional layered network structure. C-CoCP@GO was obtained by binding with GO and C-CoCP, its morphology and structure were investigated by XRD, SEM, EDS, FTIR, and TGA, which confirmed its two-dimensional stacked layered structure with high catalytic activity and large specific surface area.

Synthesis, Structural Versatility, Magnetic Properties, and I Adsorption in a Series of Cobalt(II) Metal-Organic Frameworks with a Charge-Neutral Aliphatic (O,O)-Donor Bridge.

Four new metal-organic frameworks based on cobalt(II) salts and 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide (odabco) were obtained.

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.

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.

Diastereoselective guest-shape dependent [2+2]-photodimerization of 2-cyclopenten-1-one trapped within a metal-organic framework.

UV-induced [2+2] dimerization of 2-cyclopenten-1-one and 2-methyl-2-cyclopenten-1-one was successfully carried out in a single-crystal-to-single-crystal manner within a porous metal-organic framework. Intermolecular contacts direct the orientation of the α,β-enone molecules within the host channels, which drives the subsequent photoaddition reaction in a facile and diastereoselective fashion, yielding head-to-tail dimers only.

Ultra-low limit of luminescent detection of gossypol by terbium(III)-based metal-organic framework.

The widespread use of gossypol-containing animal feed and cottonseed oil poses a great threat to water quality and livestock and human health, and there is an urgent need for a sensor for the rapid detection of trace amounts of gossypol in aqueous solutions and cottonseed oil. As a result, an unprecedented three-dimensional metal-organic framework sensor based on terbium(III) and a flexible ligand 4-(3,5-dicarboxyphenoxy)isophthalic acid (HL) was developed. Tb-MOF, {[Tb(HO)(HL)]·0.

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.

A new subclass of copper(I) hybrid emitters showing TADF with near-unity quantum yields and a strong solvatochromic effect.

We introduce here a new subclass of copper(I) hybrid emitters simultaneously containing [CuI] anions and Cu cations, separated in space by a Janus head ligand. When UV-irradiated at 298 K, these unique "Two-In-One" hybrids exhibit a short-lived green TADF with near-unity quantum yield and a strong solvatochromic effect. Moreover, they manifest a strong radioluminescence upon X-ray irradiation.

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.

Variable Dimensionality of Europium(III) and Terbium(III) Coordination Compounds with a Flexible Hexacarboxylate Ligand.

A reaction between 4,4',4″-(benzene-1,3,5-triyltris(oxy))triphthalic acid (HL) and lanthanide(III) nitrates (Ln = Eu, Tb) in water under the same conditions gave a molecular coordination compound [Tb(HL)(HO)]∙6HO in the case of terbium(III) and a one-dimensional linear coordination polymer {[Eu(HL)(HO)]∙8HO} in the case of europium(III). The crystal structures of both compounds were established by single-crystal X-ray diffraction, and they were further characterized by powder X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. The compounds demonstrated characteristic lanthanide-centered photoluminescence.

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.

Dimensionality Mediated Highly Repeatable and Fast Transformation of Coordination Polymer Single Crystals for All-Optical Data Processing.

A family of coordination polymers (CPs) based on dynamic structural elements are of great fundamental and commercial interest addressing modern problems in controlled molecular separation, catalysis, and even data processing. Herein, the endurance and fast structural dynamics of such materials at ambient conditions are still a fundamental challenge. Here, we report on the design of a series of Cu-based CPs [Cu(bImB)Cl] and [Cu(bImB)Cl] with flexible ligand bImB (1,4-bis(imidazol-1-yl)butane) packed into one- and two-dimensional (1D, 2D) structures demonstrating dimensionality mediated flexibility and reversible structural transformations.

Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu and Au@Ag Clusters Supported by tris(2-Pyridyl)phosphine.

We report herein a family of polynuclear complexes, [Au@Ag(PyP)]X and [Au@Cu(PyP)]X [X = NO, ClO, OTf, BF, SbF], containing unprecedented Au-centered Ag and Cu tetrahedral cores supported by tris(2-pyridyl)phosphine (PyP) ligands. The [Au@Ag] clusters are synthesized controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag] precursors by the reaction with Au()Cl, while the [Au@Cu] cluster is assembled through the treatment of a pre-organized [Au(PyP)] metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions.

Zn(II) and Co(II) 3D Coordination Polymers Based on 2-Iodoterephtalic Acid and 1,2-bis(4-pyridyl)ethane: Structures and Sorption Properties.

Metal-organic frameworks [M(2-I-bdc)bpe] (M = Zn(II) (), Co(II) (), 2-I-bdc = 2-iodoterephtalic acid, and bpe = 1,2-bis(4-pyridyl)ethane) were prepared and characterized by X-ray diffractometry. Both compounds retain their 3D structure after the removal of guest DMF molecules. Selectivity of sorption of different organic substrates from the gas phase was investigated for both complexes.

Three novel metal-organic frameworks with different coordination modes for trace detection of anthrax biomarkers.

Dipicolinic acid (DPA) is an anthrax biomarker. Its serious consequences make its detection a great need. In this paper, three novel metal-organic frameworks (MOFs) with different coordination modes were synthesized by a simple solvothermal method, which can be used as highly efficient fluorescence sensors for the highly selective and sensitive trace detection of DPA.

Cinnamal Sensing and Luminescence Color Tuning in a Series of Rare-Earth Metal-Organic Frameworks with Trans-1,4-cyclohexanedicarboxylate.

Three isostructural metal-organic frameworks ([Ln(phen)(NO)(chdc)]·2DMF (Ln = Y for , Eu for or Tb for ; phen = 1,10-phenanthroline; Hchdc = -1,4-cyclohexanedicarboxylic acid) were synthesized and characterized. The compounds are based on a binuclear block {M(phen)(NO)(OOCR)} assembled into a two-dime nsional square-grid network containing tetragonal channels with 26% total solvent-accessible volume. Yttrium ()-, europium ()- and terbium ()-based structures emit in the blue, red and green regions, respectively, representing the basic colors of the standard RGB matrix.