Search results for "frameworks"
showing 10 items of 120 documents
Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal–Organic Framework
2018
"Breathing" metal-organic frameworks (MOFs) that involve changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their range of potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multifunctional "breathing" frameworks. Herein, we report the continuous breathing behavior of a tetrathiafulvalene (TTF)-based MOF, namely MUV-2, showing a reversible swelling (up to ca. 40% of the volume cell) upon solvent adsorption. Importantly, the planarity of the TTF linkers is influenced by the breathing behavior of the MOF, directly impacting on its electrochemical proper…
Stimuli-responsive magnetic coordination polymers: from crystals to nanoparticles
2013
El trabajo descrito en esta tesis se enmarca en el ámbito de los polímeros de coordinación (PC). Estos sistemas representan un área importante dentro de la Química de los Materiales, siendo principalmente interesantes sus aplicaciones en catálisis, electrónica y óptica. Su origen data de principios de los años 60, donde se produjo la primera revisión de estructuras de compuestos inorgánicos que formaban cadenas.1 Los PC están formados por ligandos orgánicos y metales enlazados por enlaces de coordinación que se extienden infinitamente en 1, 2 o 3 dimensiones. En cuanto a su versatilidad química, las estructuras y propiedades varían en función de los metales o ligandos utilizados. Así pues, …
Exploring the catalytic performance of a series of bimetallic MIL-100(Fe, Ni) MOFs
2019
[EN] A series of mixed-metal Fe-III/Ni-II metal-organic frameworks (MOFs) of the MIL-100 type containing different metal ratios have been synthesized de novo, following an approach that requires tuning of the Fe-III/Ni-II reactivity. The resulting heterometallic MIL-100(Fe, Ni) materials maintain thermal, chemical and structural stability with respect to the parent MIL-100(Fe) MOF as can be deduced from various techniques. The nature and the oxidation state of the accessible metal cations have been evaluated by in situ infrared spectroscopy and extended X-ray absorption fine structure measurements. The obtained mixed-metal MOFs and the parent material have been evaluated as heterogeneous ca…
Elucidating Gating Effects for Hydrogen Sorption in MFU-4-Type Triazolate-Based Metal-Organic Frameworks Featuring Different Pore Sizes
2011
A highly porous member of isoreticular MFU-4-type frameworks, [Zn(5)Cl(4)(BTDD)(3)] (MFU-4l(arge)) (H(2)-BTDD=bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), has been synthesized using ZnCl(2) and H(2)-BTDD in N,N-dimethylformamide as a solvent. MFU-4l represents the first example of MFU-4-type frameworks featuring large pore apertures of 9.1 Å. Here, MFU-4l serves as a reference compound to evaluate the origin of unique and specific gas-sorption properties of MFU-4, reported previously. The latter framework features narrow-sized pores of 2.5 Å that allow passage of sufficiently small molecules only (such as hydrogen or water), whereas molecules with larger kinetic diameters (e.…
Blaming the Light, Claiming the Night. Actors, Issues and Effects of Lighting Conflicts in France since the 1980's
2014
International audience; Regarding environmental issues, conflictuality is a privileged way to reach the political arena. "Naming, Blaming, Claiming": three steps that make the controversy emerge, constitute the public issue, then bring it to the politi- cal agenda. These three stages are clearly identifiable in the history of night protection associative movements. These movements emerged in the 1970's in the United States of America, quickly disseminated enjoying a broader context of environmental thinking. Conflicts related to artificial lighting are structurally akin to conflicts of contradictory uses of a single resource: the night. For some - the technicists -, the night is the "good-s…
A step further in the comprehension of the magnetic coupling in gadolinium(III)-based carboxylate complexes
2013
Three new gadolinium(III) complexes of formula [Gd4(bta) 3(H2O)16]n·12nH2O (1), [Gd4(bta)3(H2O)12] n·18nH2O (2) and [Gd2(H 2bta)(bta)(H2O)2]n·4nH 2O (3) (H4bta = 1,2,4,5-benzenetetracarboxylic acid) have been synthesized and their structures determined by X-ray diffraction. 1 and 3 are three-dimensional compounds whereas 2 exhibits a two-dimensional structure. The ability of the bta4- to adopt different coordination modes accounts for these high dimensionalities although it precludes a rational structural design. The structures of 1-3 have in common the double oxo-carboxylate bridge between gadolinium(III) ions (μ-O: κ2O,O′) either as a discrete units (1 and 2) or as a chain (3) and one (3)…
Nuevos materiales moleculares de hierro(II) multipropiedad basados en el fenómeno de transición de espín
2017
En esta Tesis Doctoral se presenta la síntesis y caracterización de una serie de materiales multifuncionales de FeII que tienen como denominador común el fenómeno de transición de espín (TS). El objetivo general es investigar sinergias entre la TS y otra propiedad fisicoquímica mediante el estudio de su estructura molecular y sus propiedades magnéticas y calorimétricas, entre otras. En el Capítulo Uno se exponen los conceptos más relevantes del fenómeno TS en el cual los centros TS experimentan una conversión de espín HS↔LS (HS: estado de espín alto, LS: estado de espín bajo) en respuesta a un estímulo externo tal como temperatura, presión, luz o la presencia de analitos. En particular, una…
Hybrid Inorganic‐Organic White Light Emitting Diodes
2020
This chapter reviews the state of the art of materials, technologies, characterizations, process and challenges concerning hybrid white light‐emitting diodes (LEDs). Here, for a “hybrid LED” we mean a device based on a layer of organic phosphors (or a mix of inorganic and organic ones) pumped by a high‐energy inorganic LED. Light is emitted by a frequency down‐conversion (sometimes simply named color‐conversion) process. Benefits and weak spots of this technology are investigated with a special attention for the materials involved into the process of frequency down‐conversion, in order to envisage the future impact of the hybrid lighting technology among the well‐established inorganic ones.
Metal-Organic Frameworks as Versatile Heterogeneous Solid Catalysts for Henry Reactions
2021
Metal–organic frameworks (MOFs) have become one of the versatile solid materials used for a wide range of applications, such as gas storage, gas separation, proton conductivity, sensors and catalysis. Among these fields, one of the more well-studied areas is the use of MOFs as heterogeneous catalysts for a broad range of organic reactions. In the present review, the employment of MOFs as solid catalysts for the Henry reaction is discussed, and the available literature data from the last decade are grouped. The review is organized with a brief introduction of the importance of Henry reactions and structural properties of MOFs that are suitable for catalysis. The second part of the review dis…
Exploiting Reaction-Diffusion Conditions to Trigger Pathway Complexity in the Growth of a MOF.
2021
Coordination polymers (CPs), including metal–organic frameworks (MOFs), are crystalline materials with promising applications in electronics, magnetism, catalysis, and gas storage/separation. However, the mechanisms and pathways underlying their formation remain largely undisclosed. Herein, we demonstrate that diffusion-controlled mixing of reagents at the very early stages of the crystallization process (i.e., within ≈40 ms), achieved by using continuous-flow microfluidic devices, can be used to enable novel crystallization pathways of a prototypical spin-crossover MOF towards its thermodynamic product. In particular, two distinct and unprecedented nucleation-growth pathways were experimen…