Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Proton Conduction in Metal-Organic Frameworks and Related Modularly Built Porous Solids

Proton-conducting materials are an important component of fuel cells. Development of new types of proton-conducting materials is one of the most important issues in fuel-cell technology. Herein, we present newly developed proton-conducting materials, modularly built porous solids, including coordination polymers (CPs) or metalorganic frameworks (MOFs). The designable and tunable nature of the porous materials allows for fast development in this research field. Design and synthesis of the new types of proton-conducting materials and their unique proton-conduction properties are discussed.

Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency

Three new electron-rich metal-organic frameworks (MOF-1-MOF-3) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the -electron density of the luminescent MOFs. Single-crystal X-ray structures have revealed that these MOFs form three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron-rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF-1 and MOF-2 exhibit superior sensitivity towards 4-nitrotoluene (4-NT) and 2,4-dinitrotoluene (DNT) compared to 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB). MOF-3, on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady-state and time-resolved fluorescence quenching associated with these interactions. Determination of static Stern-Volmer constants (K-S) as well as collisional constants (K-C) has revealed that MOF-1 and MOF-2 have higher K-S values with 4-NT than with TNT, whereas for MOF-3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.

Construction of Bis-pyrazole Based Co(II) Metal-Organic Frameworks and Exploration of Their Chirality and Magnetic Properties

In continuation of our interest in pyrazole based multifunctional metal-organic frameworks (MOFs), we report herein the construction of a series of Co(II) MOFs using a bis-pyrazole ligand and various benzene polycarboxylic acids. Employment of different acids has resulted in different architectures ranging from a two-dimensional grid network, porous nanochannels with interesting double helical features such as supramolecular chicken wire, to three-dimensional diamondoid networks. One of the distinguishing features of the network is their larger dimensions which can be directly linked to a relatively larger size of the ligand molecule. Conformational flexibility of the ligand also plays a decisive role in determining both the dimensionality and topology of the final structure. Furthermore, chirality associated with helical networks and magnetic properties of two MOFs have also been investigated.

Multicomponent Assembly of Fluorescent-Tag Functionalized Ligands in Metal-Organic Frameworks for Sensing Explosives

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal organic frameworks (MOFs-12, 13, 23, and 123) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by singlecrystal XRD. Single-crystal structures of the MOFs-12 and 13 showed the formation of three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron-rich MOFs were utilized for detection of ex- plosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6-trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6-trinitrotoluene (TNT).

A smart approach to achieve an exceptionally high loading of metal nanoparticles supported by functionalized extended frameworks for efficient catalysis

The problem associated with metal nanoparticle (NP) agglomeration when trying to achieve a high loading amount has been solved by a new method of functionalization of MOFs' pores with terminal alkyne moieties. The alkynophilicity of the Au3+ ions has been utilized successfully for an exceptionally high loading (similar to 50 wt%) of Au-NPs on supported functionalized MOFs.

Redox-Active Metal-Organic Frameworks: Highly Stable Charge-Separated States through Strut/Guest-to-Strut Electron Transfer

Molecular organization of donor and acceptor chromophores in self-assembled materials is of paramount interest in the field of photovoltaics or mimicry of natural light-harvesting systems. With this in mind, a redox-active porous interpenetrated metal-organic framework (MOF), {Cd(bpdc)(bpNDI)]4.5H(2)ODMF}(n) (1) has been constructed from a mixed chromophoric system. The -oxo-bridged secondary building unit, {Cd-2(-OCO)(2)}, guides the parallel alignment of bpNDI (N,N-di(4-pyridyl)-1,4,5,8-naphthalenediimide) acceptor linkers, which are tethered with bpdc (bpdcH(2)=4,4-biphenyldicarboxylic acid) linkers of another entangled net in the framework, resulting in photochromic behaviour through inter-net electron transfer. Encapsulation of electron-donating aromatic molecules in the electron-deficient channels of 1 leads to a perfect donor-acceptor co-facial organization, resulting in long-lived charge-separated states of bpNDI. Furthermore, 1 and guest encapsulated species are characterised through electrochemical studies for understanding of their redox properties.

Interpenetrated and Catenated Zinc Thiosulfates Frameworks with dia and qtz Nets: Synthesis, Structure, and Properties

Reactions between Zn(NO3)(2)center dot 6H(2)O, Na2S2O3, 4,4'-bipyridine (bpy), 1,2-bis(4-pyridyl)ethene (bpe), 1,2-bis (4-pyridyl) ethane (bpa), and 1,3-bis(4-pyridyl)propane (bpp) under solvothermal conditions resulted in four new zinc thiosulfate hybrid compounds. Compound I has four-membered zinc thiosulfate rings connected by the ligand, 1,3-bis(4-pyridyl)propane (bpp) forming a two-dimensional structure. Compounds II-IV have one-dimensional zinc thiosulfate chains connected by the ligands, bpy (II), bpe (III), and bpa (IV) giving rise to three-dimensional structures. All the four-structures exhibit 3-fold interpenetration. Proton conductivity studies indicate reasonable proton mobility at 34 degrees C and at 98% relative humidity. The compounds also exhibit Lewis acid character and good photocatalytic activity for the decomposition of cationic dyes.

Los dilemas de la acción colectiva global. Un estudio de caso : el movimiento sindical en el MERCOSUR (1991-2012)

Resumen: Este trabajo analiza la acción colectiva sindical postnacional en el MERCOSUR en un período histórico signado por profundas mutaciones políticas, económicas, y productivas sociales (1991-2012) a partir de los relatos y representaciones de sus protagonistas. El trabajo cualitativo intentará explicar la configuración del sindicalismo internacional en la globalización, y describir las estrategias del movimiento obrero mercosureño. La metodología cualitativa ilustra un trabajo de campo a partir de entrevistas en profundidad a 34 sindicalistas del Mercosur, y entrevistas adicionales a tres representantes de la Confederación Sindical de las Américas, dos empresarios del Mercosur, un especialista académico en la dimensión sociolaboral de la integración regional y un representante de la OIT en la región. La metodología de análisis e interpretación de dichas entrevistas ha sido la teoría fundamentada, entendida como la técnica más idónea de aprehender los procesos sociales a través de las voces de los líderes obreros, comprender su realidad, sus representaciones y sistema de valores, sus ideas y su acción colectiva. La literatura de los movimientos sociales en la globalización capitalista ha puesto el énfasis en la emergencia de nuevos colectivos cuyos reclamos se concentran en el reconocimiento (Fraser y Honneth, 2006) de sus identidades que el modelo fordista de producción pareció invisibilizar y soslayar ante la primacía de las prácticas económicas y demandas distributivas. Esta tesis conjuga una perspectiva dualista y demuestra que las estrategias de reconocimiento y las reivindicaciones de redistribución de tipo clasista se resignificaron en el escenario postnacional a través de la Coordinadora de Centrales Sindicales del Cono Sur –CCSCS- (subregional) y, con un desarrollo menor: los Sindicatos Globales (FSI, GUFs) en la acción sectorial [1991-2012]. Para arribar al núcleo configurativo de sus representaciones y su sistema de valores, la investigación transitó por los sentidos y significados del trabajo, las mutaciones productivas y de las condiciones del trabajo, las teorías del fin del trabajo, la precarización y la representación de los trabajadores más frágiles: mujeres, jóvenes y migrantes. En un segundo orden se interpeló sobre la gobernanza mundial, los organismos internacionales, el régimen normativo internacional, la civilización capitalista, para luego abordar el estudio específico del Mercosur y la acción obrera en dicho proceso. El núcleo determinó que para los representantes obreros la acción colectiva sindical debe ser postnacional y su objetivo es limitar la globalización capitalista neoliberal. La CCSCS conformó desde sus inicios un movimiento capaz de elevarse al rango supranacional para representar la voz de los trabajadores del MERCOSUR. La pluralidad configuró su mayor virtud durante sus primeros 20 años, reconociendo una experiencia de aprendizaje de tolerancia y respeto, que ellos definen como la unidad en la diversidad. Esta entidad constituye un patrimonio único como paradigma del sindicalismo postnacional. Los sindicatos del Cono Sur adoptaron diversas modalidades de acción colectiva: a) reactiva (con repertorios de insubordinación, de lucha y resistencia al modelo neoliberal), b) proactiva (con repertorios de incidencia normativa en el MERCOSUR) y c) participativa (con repertorios de producción propositiva de incidencia en la dimensión social del MERCOSUR). Su acción colectiva reactiva, normativa y propositiva fue eficaz a mediano plazo para participar e incidir en el MERCOSUR, crear una dimensión social del bloque y dotar de derechos normativos a los ciudadanos de la región. Su acción tuvo un sentido político de gran poder instituyente, con capacidad movilización y alta exposición pública. Sin embargo, en la segunda década su lógica de construcción quedó subordinada a los procesos nacionales y a los partidos gobernantes, dejó de ser performativa y de creación política, dirimiéndose en la esfera social junto a otros movimientos sociales emergentes, y provocó un ciclo de desmovilización. Simultáneamente, emergió con fuerza otra modalidad de sindicalismo postnacional con la fusión y refundación de los Sindicatos Globales. Su acción sectorial contribuye a restaurar las demandas de distribución que habían quedado soslayadas, pero esta tesis manifiesta que los protagonistas afirman que sus marcos de acción colectiva deberán ser conjuntos para ser exitosa. El sindicalismo postnacional en el MERCOSUR se define a sí mismos como agente de desarrollo, protagonista del modelo socioproductivo, pero también como vehículo partícipe de la democracia y de una matriz sustentable de desarrollo

Case study: Mastering the governance of technology

Case study on how the Heart of Worcestershire College is leading a project with four other colleges to support college governors in making confident, effective and well-informed decisions on the investment, innovation and development of technology use to support learning.