Gas Sorption and Luminescence Properties of a Terbium(III)-Phosphine Oxide Coordination Material with Two-Dimensional Pore Topology

The structure, stability, gas sorption properties and luminescence behaviour of a new lanthanide-phosphine oxide coordination material are reported. The polymer PCM-15 is based on Tb(III) and tris(p-carboxylated) triphenylphosphine oxide and has a 5,5-connected net topology. It exhibits an infinite three-dimensional structure that incorporates an open, two-dimensional pore structure. The material is thermally robust and remains crystalline under high vacuum at 150 degrees C. When desolvated, the solid has a CO2 BET surface area of 1187 m(2) g(-1) and shows the highest reported uptake of both O-2 and H-2 at 77 K and 1 bar for a lanthanide-based coordination polymer. Isolated Tb(III) centres in the as-synthesized polymer exhibit moderate photoluminescence. However, upon removal of coordinated OH2 ligands, the luminescence intensity was found to approximately double; this process was reversible. Thus, the Tb(III) centre was used as a probe to detect directly the desolvation and resolvation of the polymer.Welch Foundation F-1738, F-1631National Science Foundation 0741973, CHE-0847763Chemistr

CO2 Adsorption Properties of a Ca(II)-Based Organophosphonium Coordination Material

PCM-14 is a dense coordination polymer formed from Ca(II) and an unusual organophosphonium ligand. The dehydrated framework contains 3-coordinate Ca(II) sites within catenated, chiral 3,3-connected nets. PCM-14 exhibits a stark CO2 sorption selectivity over H-2, N-2 and O-2. The maximum CO2 uptake was shown to be highly sensitive to the material pretreatment evacuation temperature.Welch Foundation F-1738Chemistr

Statistical distribution of binary ligands within rhodium-organic octahedra tunes microporosity in their assemblies

Structure-porosity relationships for metal-organic polyhedra (MOPs) are hardly investigated because they tend to be amorphized after activation, which inhibits crystallographic characterization. Here, we show a mixed-ligand strategy to statistically distribute two distinct carbazole-type ligands within rhodium-based octahedral MOPs, leading to systematic tuning of the microporosity in the resulting amorphous solids

Separation of CO2 from CH4 and CO2 capture in the presence of water vapour in NOTT-400

From a binary equimolar gas-mixture of CO2 and CH4, NOTT-400 shows CO2 separation from CH4. By kinetic uptake experiments, this material confirms a maximum of 4.3 wt% CO2 capture at 30 8C and a significant 2-fold increase (B9.3 wt%) in CO2 capture under 40% relative humidity of water vapour.Fil: Ibarra, Ilich A.. Universidad Nacional Autonoma de Mexico. Instituto de Investigaciones en Materiales; MéxicoFil: Pfeiffer, Heriberto. Universidad Nacional Autonoma de Mexico. Instituto de Investigaciones en Materiales; MéxicoFil: Basaldella, Elena Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina. Universidad Tecnologica Nacional. CITEMA; ArgentinaFil: Sánchez-Camacho, Pedro. Universidad Nacional Autonoma de Mexico. Instituto de Investigaciones en Materiales; MéxicoFil: Lara- García, Hugo A.. Universidad Nacional Autonoma de Mexico. Instituto de Investigaciones en Materiales; MéxicoFil: González Estefan, Juan Hugo. Universidad Nacional Autonoma de Mexico. Instituto de Investigaciones en Materiales; MéxicoFil: González, Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentin

Modulated self-assembly of three flexible Cr(III) PCPs for SO2 adsorption and detection

Modulated self-assembly protocols are used to develop facile, HF-free syntheses of the archetypal flexible PCP, MIL-53(Cr), and novel isoreticular analogues MIL-53(Cr)-Br and MIL-53(Cr)-NO2. All three PCPs show good SO2 uptake (298 K, 1 bar) and high chemical stabilities against dry and wet SO2. Solid-state photoluminescence spectroscopy indicates all three PCPs exhibit turn-off sensing of SO2, in particular MIL-53(Cr)-Br, which shows a 2.7-fold decrease in emission on exposure to SO2 at room temperature, indicating potential sensing applications

Confined benzene within InOF-1: Contrasting CO2 and SO2 capture behaviours

The confinement of small amounts of benzene in InOF-1 (Bz@InOF-1) shows a contradictory behavior in the capture of CO2 and SO2. While the capture of CO2 is increased 1.6 times, compared to the pristine material, the capture of SO2 shows a considerable decrease. To elucidate these behaviors, the interactions of CO2 and SO2 with Bz@InOF-1 were studied by DFT periodical calculations postulating a plausible explanation: (a) in the case of benzene and CO2, these molecules do not compete for the preferential adsorption sites within InOF-1, providing a cooperative CO2 capture enhancement and (b) benzene and SO2 strongly compete for these preferential adsorption sites inside the MOF material, reducing the total SO2 capture

A Robust and Biocompatible Bismuth Ellagate MOF Synthesized Under Green Ambient Conditions

The first bioinspired microporous metal-organic framework (MOF) synthesized using ellagic acid, a common natural antioxidant and polyphenol building unit, is presented. Bi2O(H2O)2(C14H2O8)\ub7nH2O (SU-101) was inspired by bismuth phenolate metallodrugs, and could be synthesized entirely from nonhazardous or edible reagents under ambient aqueous conditions, enabling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid was sourced from tree bark and pomegranate hulls, respectively. Biocompatibility and colloidal stability were confirmed by in vitro assays. The material exhibits remarkable chemical stability for a bioinspired MOF (pH = 2-14, hydrothermal conditions, heated organic solvents, biological media, SO2 and H2S), attributed to the strongly chelating phenolates. A total H2S uptake of 15.95 mmol g-1 was recorded, representing one of the highest H2S capacities for a MOF, where polysulfides are formed inside the pores of the material. Phenolic phytochemicals remain largely unexplored as linkers for MOF synthesis, opening new avenues to design stable, eco-friendly, scalable, and low-cost MOFs for diverse applications, including drug delivery

Controlled transdermal release of antioxidant ferulate by a porous Sc(III) MOF

The Sc(III) MOF-type MFM-300(Sc) is demonstrated in this study to be stable under physiological conditions (PBS), biocompatible (to human skin cells), and an efficient drug carrier for the long-term controlled release (through human skin) of antioxidant ferulate. MFM-300(Sc) also preserves the antioxidant pharmacological effects of ferulate while enhancing the bio-preservation of dermal skin fibroblasts, during the delivery process. These discoveries pave the way toward the extended use of Sc(III)-based MOFs as drug delivery systems (DDSs)

Synthesis of metal-organic frameworks by continuous flow

A continuous flow process for the synthesis of a metal-organic framework using only water as the reaction medium and requiring only short residence times is described. This affords a new route to scale-up of materials incorporating many of the principles of green chemistry. The process is demonstrated by the synthesis MIL-53(Al) via continuous flow reaction requiring only 5-6 minutes with a space time yield of 1300 kg m-3 d-1. We have demonstrated the synthesis of 500 g of MIL-53(Al) using this process, which can be scaled-up further by simply feeding further solutions of metal salt and ligand through the reactor. The product has a higher surface area and a better colour than a commercially produced sample of this MOF. In addition, a new and effective method for the extraction of terephthalic acid from within the pores of MIL-53(Al) using supercritical ethanol has been developed, representing a new methodology for activation and removal of substrates from porous hosts

Introduction to celebrating Latin American talent in chemistry

In celebration of the excellence and breadth of Latin American research achievements across the chemical sciences, we are delighted to present an introduction to the themed collection, Celebrating Latin American talent in chemistry. [Image: see text