Observation of a Reversible Order-Order Transition in a Metal-Organic Framework - Ionic Liquid Nanocomposite Phase-Change Material.

Metal-organic framework (MOF) composite materials containing ionic liquids (ILs) have been proposed for a range of potential applications, including gas separation, ion conduction, and hybrid glass formation. Here, an order transition in an IL@MOF composite is discovered using CuBTC (copper benzene-1,3,5-tricarboxylate) and [EMIM][TFSI] (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide). This transition - absent for the bare MOF or IL - provides an extended super-cooling range and latent heat at a capacity similar to that of soft paraffins, in the temperature range of ≈220 °C.

Unravelling the Molecular Structure and Confining Environment of an Organometallic Catalyst Heterogenized within Amorphous Porous Polymers.

The catalytic activity of multifunctional, microporous materials is directly linked to the spatial arrangement of their structural building blocks. Despite great achievements in the design and incorporation of isolated catalytically active metal complexes within such materials, a detailed understanding of their atomic-level structure and the local environment of the active species remains a fundamental challenge, especially when these latter are hosted in non-crystalline organic polymers. Here, we show that by combining computational chemistry with pair distribution function analysis, Xe NMR, and Dynamic Nuclear Polarization enhanced NMR spectroscopy, a very accurate description of the molecular structure and confining surroundings of a catalytically active Rh-based organometallic complex incorporated inside the cavity of amorphous bipyridine-based porous polymers is obtained.

Thermal Expansion of Metal-Organic Framework Crystal-Glass Composites.

Metal-organic framework crystal-glass composites (MOF CGCs) are a class of materials comprising a crystalline framework embedded within a MOF glass matrix. Herein, we investigate the thermal expansion behavior of three MOF CGCs, incorporating two flexible (MIL-53(Al) and MIL-118) and one rigid (UL-MOF-1) MOF within a ZIF-62 glass matrix. Specifically, variable-temperature powder X-ray diffraction data and thermomechanical analysis show the suppression of thermal expansivity in each of these three crystalline MOFs when suspended within a ZIF-62 glass matrix.

Stepwise collapse of a giant pore metal-organic framework.

Defect engineering is a powerful tool that can be used to tailor the properties of metal-organic frameworks (MOFs). Here, we incorporate defects through ball milling to systematically vary the porosity of the giant pore MOF, MIL-100 (Fe). We show that milling leads to the breaking of metal-linker bonds, generating additional coordinatively unsaturated metal sites, and ultimately causes amorphisation.

Functional Group Mapping by Electron Beam Vibrational Spectroscopy from Nanoscale Volumes.

Vibrational spectroscopies directly record details of bonding in materials, but spatially resolved methods have been limited to surface techniques for mapping functional groups at the nanoscale. Electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope presents a route to functional group analysis from nanoscale volumes using transmitted subnanometer electron probes. Here, we now use vibrational EELS to map distinct carboxylate and imidazolate linkers in a metal-organic framework (MOF) crystal-glass composite material.

Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites.

Metal-organic framework crystal-glass composites (MOF-CGCs) are materials in which a crystalline MOF is dispersed within a MOF glass. In this work, we explore the room-temperature stabilization of the open-pore form of MIL-53(Al), usually observed at high temperature, which occurs upon encapsulation within a ZIF-62(Zn) MOF glass matrix. A series of MOF-CGCs containing different loadings of MIL-53(Al) were synthesized and characterized using X-ray diffraction and nuclear magnetic resonance spectroscopy.

Metal-organic framework crystal-glass composites.

The majority of research into metal-organic frameworks (MOFs) focuses on their crystalline nature. Recent research has revealed solid-liquid transitions within the family, which we use here to create a class of functional, stable and porous composite materials. Described herein is the design, synthesis, and characterisation of MOF crystal-glass composites, formed by dispersing crystalline MOFs within a MOF-glass matrix.

Novel metal-organic framework materials: blends, liquids, glasses and crystal-glass composites.

Metal-organic frameworks (MOFs) are often, and incorrectly, believed to be purely crystalline solids. This Feature Article highlights a selection of highly disordered MOF-based materials. This disorder gives rise to numerous possibilities in the fabrication of new MOF materials, and presents an alternative method of novel materials discovery, outside of the synthesis of increasingly complex crystalline structures.

Structural evolution in a melt-quenched zeolitic imidazolate framework glass during heat-treatment.

A pronounced enthalpy release occurs around 1.38Tg in the prototypical metal-organic framework glass formed from ZIF-4 [Zn(C3H3N2)2], but there is no sign for any crystallization (i.e.

Metal-organic framework glasses with permanent accessible porosity.

To date, only several microporous, and even fewer nanoporous, glasses have been produced, always via post synthesis acid treatment of phase separated dense materials, e.g. Vycor glass.

Publisher Correction: Liquid phase blending of metal-organic frameworks.

The original version of this Article contained an error in Figure 1b, where the blue '(ZIF-4-Zn) (ZIF-62) blend' data curve was omitted from the enthalpy response plot. This has now been corrected in both the PDF and HTML versions of the Article.

Thermodynamic features and enthalpy relaxation in a metal-organic framework glass.

In this work, we explore the thermodynamic evolution in a melt-quenched metal-organic framework glass, formed from ZIF-62 upon heating to the melting point (Tm), and subsequent enthalpy relaxation. The temperature dependence of the difference in Gibbs free energy between the liquid and crystal states of ZIF-62 in the temperature range from the glass transition temperature (Tg) to Tm is found to be weaker than those of other types of glasses, e.g.

Liquid phase blending of metal-organic frameworks.

The liquid and glass states of metal-organic frameworks (MOFs) have recently become of interest due to the potential for liquid-phase separations and ion transport, alongside the fundamental nature of the latter as a new, fourth category of melt-quenched glass. Here we show that the MOF liquid state can be blended with another MOF component, resulting in a domain structured MOF glass with a single, tailorable glass transition. Intra-domain connectivity and short range order is confirmed by nuclear magnetic resonance spectroscopy and pair distribution function measurements.