Silver 4,4'-Vinylenedipyridine Coordination Polymers: Linker Effects on Formation Thermodynamics and Anion Exchange.

Four new and one previously reported silver 4,4'-vinylenedipyridine (Vpe) coordination polymers were tested as anion exchange materials to assess their potential for pollutant sequestration and compared to analogous silver 4,4'-bipyridine (bipy) coordination polymers. The materials were synthesized using nitrate, tetrafluoroborate, perchlorate, perrhenate, or chromate as the anion to produce cationic coordination polymers with solubilities ranging from 0.0137(7) to 0.

Silver 2,4'-Bipyridine Coordination Polymer for the High-Capacity Trapping of Perrhenate, A Pertechnetate Surrogate.

Pertechnetate, the most stable form of the radionuclide Tc in aerobic aqueous systems, is a hazardous anion present in nuclear waste. Its high mobility in water makes the remediation of the anion challenging. In the past decade, significant effort has been placed into finding materials capable of adsorbing this species.

Selective Chromium(VI) Trapping by an Acetate-Releasing Coordination Polymer.

We report the high-capacity and selective uptake of Cr(VI) from water using the coordination polymer silver bipyridine acetate (SBA, [Ag(4,4'-bipy)][CHCO]·3HO). Cr capture involves the release of acetate, and we have structurally characterized two of the product phases that form: silver bipyridine chromate (SBC, SLUG-56, [Ag(4,4'-bipy)][CrO]·3.5HO) and silver bipyridine dichromate (SBDC, SLUG-57, [Ag(4,4'-bipy)][CrO]·HO).

A crystal-structural study of Pauling-Corey rippled sheets.

Following the seminal theoretical work on the pleated β-sheet published by Pauling and Corey in 1951, the rippled β-sheet was hypothesized by the same authors in 1953. In the pleated β-sheet the interacting β-strands have the same chirality, whereas in the rippled β-sheet the interacting β-strands are mirror-images. Unlike with the pleated β-sheet that is now common textbook knowledge, the rippled β-sheet has been much slower to evolve.

A Cationic Silver Pyrazine Coordination Polymer with High Capacity Anion Uptake from Water.

We report the first example of linker modification for an N-donor Ag-based cationic material while maintaining and in some cases increasing the anion exchange capacity. Cationic silver(I) pyrazine nitrate selectively traps harmful oxo-anions from water such as permanganate, perrhenate and a variety of α,ω-alkanedicarboxylates. We chose these anions as initial examples of exchange for potential water purification.

Exchange Capability of Cationic Silver 4,4'-Bipyrdine Materials for Potential Water Remediation: Structure, Stability, and Anion Exchange Properties.

An in-depth study of the class of cationic materials [Ag(4,4'-bipy)][X] (where X = CHCO, NO, BF, ClO, and MnO) has led to key insights on the relationship between anion hydration energy, material structure, solubility, and stability. Since these materials show promise for their potential as water remediation tools, understanding their properties in detail is of significant importance. The structure of the starting and ending materials is the main driving force behind the resultant stability and solubility and can be successfully used to predict the ion exchange capabilities.

Desulfurization of JP-8 jet fuel: challenges and adsorptive materials.

The desulfurization of JP-8 (Jet Propellant 8) fuel is of interest to the U.S. military because of its potential use as a fuel source for solid oxide fuel cells (SOFCs).

Anion exchange dynamics in the capture of perchlorate by a cationic Ag-based MOF.

We report a detailed study of the host-guest interaction for a cationic metal-organic framework that can reversibly capture perchlorate. The structural transformation and flexibility of silver 4,4'-bipyridine nitrate (SBN) upon formation of silver 4,4'-bipyridine perchlorate (SBP) was evaluated by monitoring the anion exchange dynamics using a combination of powder X-ray diffraction (PXRD) with multinuclear C, N and Ag solid-state NMR spectra at different time intervals of the anion exchange. The structural transformation from SBN to SBP is complete within 70 minutes and was determined to take place by a solvent-mediated process.

Reversible, Selective Trapping of Perchlorate from Water in Record Capacity by a Cationic Metal-Organic Framework.

We report the capture of ppm-level aqueous perchlorate in record capacity and kinetics via the complete anion exchange of a cationic metal-organic framework. Ambient conditions were used for both the synthesis of silver 4,4'-bipyridine nitrate (SBN) and the exchange, forming silver 4,4'-bipyridine perchlorate (SBP). The exchange was complete within 90 min, and the capacity was 354 mg/g, representing 99% removal.

Erbium hydroxide ethanedisulfonate: a cationic layered material with organic anion exchange capability.

We describe a cationic erbium-based material [Er12(OH)29(H2O)5][O3SCH2CH2SO3]3.5·5H2O. As synthesized, the material is water stable and capable of complete organic anion exchange for a variety of α,ω-alkanedicarboxylates.

Light-triggered carbon monoxide delivery with Al-MCM-41-based nanoparticles bearing a designed manganese carbonyl complex.

A photoactive manganese carbonyl complex namely, fac-[Mn(pqa)(CO)]ClO (abbreviated as {Mn-CO}, pqa = (2-pyridylmethyl)(2-quinolylmethyl)amine) has been incorporated in the pores of 60 nm mesoporous Al-MCM-41 nanoparticles. Strong electrostatic interactions with the negatively charged walls of the aluminosilicate host entrap the cationic carbonyl complex in the resulting material {Mn-CO}@Al-MCM-41 which has been characterized by various physical techniques and chemical analysis. The sample morphology and microstructure of the material have been established by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Solvothermal synthesis and characterization of two inorganic-organic hybrid materials based on barium.

Two metal-organic frameworks containing barium were synthesized hydrothermally and investigated for their catalytic properties. Ba(2)F(2)[O(3)SC(2)H(4)SO(3)] has barium fluoride layers linked by organic 1,2-ethanedisulfonate molecules. Ba[O(3)SC(2)H(4)SO(3)] has discrete barium centers arranged in layers and connected covalently by ethanedisulfonate bridges.

A cationic antimonite chain templated by sulfate: [Sb6O7(4+)][(SO4(2-))2].

An extended metal oxide possessing a cationic charge on the host has been synthesized by hydrothermal methods. The structure consists of 1D antimony oxide [Sb(6)O(7)](4+) chains with a new structural motif of four Sb atoms wide and unprotonated sulfate anions between the chains. The material was characterized by powder and single-crystal X-ray diffraction.

Anion exchange of the cationic layered material [Pb2F2]2+.

We demonstrate the complete exchange of the interlamellar anions of a 2-D cationic inorganic material. The α,ω-alkanedisulfonates were exchanged for α,ω-alkanedicarboxylates, leading to two new cationic materials with the same [Pb(2)F(2)](2+) layered architecture. Both were solved by single crystal X-ray diffraction and the transformation also followed by in situ optical microscopy and ex situ powder X-ray diffraction.

Light-triggered eradication of Acinetobacter baumannii by means of NO delivery from a porous material with an entrapped metal nitrosyl.

A photoactive manganese nitrosyl, namely [Mn(PaPy(3))(NO)](ClO(4)) ({Mn-NO}), has been loaded into the columnar pores of an MCM-41 host. Strong interaction between the polar nitrosyl and the -OH groups on the host wall leads to excellent entrapment of the NO donor within the porous host. With the aluminosilicate-based host (Al-MCM-41), the loading is further enhanced due to electrostatic interaction of the cationic species with the aluminum sites.

A new paradigm for anion trapping in high capacity and selectivity: crystal-to-crystal transformation of cationic materials.

We describe a new methodology to the selective trapping of priority pollutants that occur inherently as oxo-anions (e.g., perchlorate, chromate, arsenate, pertechnetate, etc.

Two cationic metal-organic frameworks based on cadmium and α,ω-alkanedisulfonate anions and their photoluminescent properties.

We have successfully synthesized three cadmium-based metal-organic frameworks by utilizing two separate organic linkers to direct the structure. The first material is a three-dimensional neutral framework based on 2D cadmium ethanedisulfonate layers pillared by a 4,4'-bipyridine linker. The other two materials are 3D cationic frameworks and are the first with propanedisulfonate and butanedisulfonate as extraframework charge balancing anions.

Hydrothermal synthesis of two cationic bismuthate clusters: an alkylenedisulfonate bridged hexamer, [Bi6O4(OH)4(H2O)2][(CH2)2(SO3)2]3 and a rare nonamer templated by triflate, [Bi9O8(OH)6][CF3SO3]5.

This paper reports the synthesis, characterization, and application of two cationic bismuthate clusters by anion templating. The compounds were synthesized under mild hydrothermal treatment and characterized by powder and single-crystal X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The first material consists of a cationic hexanuclear bismuthate cluster octahedral in geometry and linked by 1,2-ethanedisulfonate molecules.

Reversible anion exchange and catalytic properties of two cationic metal-organic frameworks based on Cu(I) and Ag(I).

We report the synthesis and characterization of two Ag(I)/Cu(I)-based cationic metal-organic frameworks and their application in both heterogeneous catalysis and anion exchange. The Cu(I)-based material was designed from our previously reported Ag(I) cationic topology. Both structures consist of cationic layers with pi-pi stacked chains of alternating metal and 4,4'-bipyridine.

Polymer-templated nanospider TiO(2) thin films for efficient photoelectrochemical water splitting.

We have discovered a facile and inexpensive approach to fabricate "nanospider" TiO(2) thin films with not only an amazing morphology but highly efficient water splitting to produce hydrogen. Our method employs benzene-swollen poly(ethylene glycol) as a sacrificial organic polymer to template the semiconductor thin film. The synthesized TiO(2) thin films are highly crystalline with optimized particle and channel size to enhance the liquid-semiconductor junction interaction.

A metal-organic framework via the reaction of benzoate with a cationic inorganic material.

Our research group previously reported a two-dimensional cationic inorganic material (BING-5, Pb(3)F(5)NO(3)) where nitrate resides in the interlamellar space and can be anion exchanged. Investigation of the possible exchange of nitrate for benzoate led to the discovery of a layered metal-organic framework, lead benzoate hydrate [Pb(C(6)H(5)CO(2))(2)(OH(2))]. The compound crystallizes as colourless plates in the monoclinic space group P2(1)/c.

Cationic inorganic materials for anionic pollutant trapping and catalysis.

Despite their vast industrial importance, almost all extended inorganic synthetic structures and naturally occurring minerals adopt a neutral or anionic charge. This tutorial review describes the current knowledge of inorganic materials that bear a positive charge on the host. The best-known example is the family of clays known as layered double hydroxides, and other limited examples also exist.

Polymer gel templating of free-standing inorganic monoliths for photocatalysis.

We have developed a simple, low-cost process to fabricate free-standing porous metal oxide monoliths. Various swollen polymers and hydrogels possessing an open network structure are infiltrated with pure liquid metal alkoxide. Hydrolysis followed by chemical or thermal degradation of the polymer leads to bulk porous monoliths, TiO2 and SiO2 as initial examples.

Two related gadolinium aquo carbonate 2-D and 3-D structures and their thermal, spectroscopic, and paramagnetic properties.

We report two new extended inorganic materials based on gadolinium. The first, [Gd(CO(3))(2)H(2)O][NH(4)], consists of negatively charged 2-D sheets of gadolinium carbonate with one coordinated water molecule and an ammonium cation between the layers. The coordinated water and one carbonate extend into the interlayer space, connecting the layers via an extensive hydrogen bonding network which includes the ammonium ions.