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Themed collection Flexibility and Disorder in Metal-Organic Frameworks

43 items
Editorial

Flexibility and disorder in metal–organic frameworks

Welcome to this themed issue of Dalton Transactions entitled ‘Flexibility and Disorder in Metal–Organic Frameworks’.

Graphical abstract: Flexibility and disorder in metal–organic frameworks
Perspective

Defects and disorder in metal organic frameworks

The wide-ranging properties of metal organic frameworks (MOFs) rely in many cases on the presence of defects within their structures and the disorder that is inevitably associated with such defects.

Graphical abstract: Defects and disorder in metal organic frameworks
Perspective

Flexible MOFs under stress: pressure and temperature

In the recent past an enormous number of Metal–Organic Framework type compounds (MOFs) have been synthesized.

Graphical abstract: Flexible MOFs under stress: pressure and temperature
Perspective

Origin of highly active metal–organic framework catalysts: defects? Defects!

This article provides a comprehensive review of the nature of catalytic sites in MOFs.

Graphical abstract: Origin of highly active metal–organic framework catalysts: defects? Defects!
Perspective

Structural flexibility in crystallized matter: from history to applications

The large reversible flexibility of hybrid crystallized matter is relatively new.

Graphical abstract: Structural flexibility in crystallized matter: from history to applications
Open Access Perspective

Neutral N-donor ligand based flexible metal–organic frameworks

This short review focuses on the flexibility aspect of MOFs based on neutral N-donor ligands with representative examples concerning the structural aspects and the subsequent properties induced by the reorganization of the frameworks.

Graphical abstract: Neutral N-donor ligand based flexible metal–organic frameworks
Communication

Adsorption deformation of microporous composites

We demonstrate a theoretical model to describe the behavior of flexible adsorbent materials, or soft porous crystals, when used in practical applications as nanostructured composites such as core–shell particles or mixed matrix membranes.

Graphical abstract: Adsorption deformation of microporous composites
Open Access Communication

Postsynthetic bromination of UiO-66 analogues: altering linker flexibility and mechanical compliance

Single-crystal to single-crystal post synthetic bromination of unsaturated carbon–carbon bonds in two related zirconium metal–organic frameworks leads to structures with lower elastic moduli.

Graphical abstract: Postsynthetic bromination of UiO-66 analogues: altering linker flexibility and mechanical compliance
Communication

Freeze-drying synthesis of an amorphous Zn2+ complex and its transformation to a 2-D coordination framework in the solid state

An amorphous and metastable precursor for a Zn two-dimensional coordination framework was synthesised via freeze drying.

Graphical abstract: Freeze-drying synthesis of an amorphous Zn2+ complex and its transformation to a 2-D coordination framework in the solid state
Paper

Molecular separations with breathing metal–organic frameworks: modelling packed bed adsorbers

This work proposes a general strategy to model the adsorption behavior of phase changing metal–organic framework (MOF) adsorbents during column separations.

Graphical abstract: Molecular separations with breathing metal–organic frameworks: modelling packed bed adsorbers
Paper

Site-specific metal and ligand substitutions in a microporous Mn2+-based metal–organic framework

Mixed-ligand syntheses and post-synthetic metal exchange performed on the Mn3L3 structure type results in site-specific manipulations to the framework structure.

Graphical abstract: Site-specific metal and ligand substitutions in a microporous Mn2+-based metal–organic framework
Open Access Paper

Tuning the flexibility in MOFs by SBU functionalization

A new approach for the fine tuning of flexibility in MOFs, involving functionalization of the secondary building unit, is presented.

Graphical abstract: Tuning the flexibility in MOFs by SBU functionalization
Open Access Paper

Second harmonic generation microscopy reveals hidden polar organization in fluoride doped MIL-53(Fe)

Doping of MIL-53(Fe) with fluoride atoms introduces a polar organization in the structure when guest molecules are present.

Graphical abstract: Second harmonic generation microscopy reveals hidden polar organization in fluoride doped MIL-53(Fe)
Paper

Assessment of the energetic performances of various ZIFs with SOD or RHO topology using high pressure water intrusion–extrusion experiments

The energetic performances of various ZIFs with SOD or RHO topology were evaluated by water intrusion–extrusion experiments under high pressure. The effects of the metal cation nature, the type of linker and the topology are discussed.

Graphical abstract: Assessment of the energetic performances of various ZIFs with SOD or RHO topology using high pressure water intrusion–extrusion experiments
Paper

Local structure of the metal–organic perovskite dimethylammonium manganese(II) formate

Total neutron scattering data suggest new geometries for transient hydrogen bonding in a disordered metal–organic framework.

Graphical abstract: Local structure of the metal–organic perovskite dimethylammonium manganese(ii) formate
Paper

Flexibility in MOFs: do scalar and group-theoretical counting rules work?

Counting rules derived from mechanical engineering and rigidity theory are applied to MOFs. Scalar versions fail to predict flexibility, but group-theoretical variant succeed. The algorithm is presented in detail and two examples are solved step-by-step.

Graphical abstract: Flexibility in MOFs: do scalar and group-theoretical counting rules work?
Paper

Defects in metal–organic frameworks: a compromise between adsorption and stability?

Defect engineering has arisen as a promising approach to tune and optimise the adsorptive performance of metal–organic frameworks.

Graphical abstract: Defects in metal–organic frameworks: a compromise between adsorption and stability?
Paper

Automated design of flexible linkers

This paper presents a method for the systematic and automated design of flexible organic linkers for construction of metal organic-frameworks (MOFs) in which flexibility, compliance, or other mechanically exotic properties originate at the linker level rather than from the framework kinematics.

Graphical abstract: Automated design of flexible linkers
Paper

Coarse graining of force fields for metal–organic frameworks

We have adapted our genetic algorithm based optimization approach, originally developed to generate force field parameters from quantum mechanic reference data, to derive a first coarse grained force field for a MOF, taking the atomistic MOF-FF as a reference.

Graphical abstract: Coarse graining of force fields for metal–organic frameworks
Paper

Impact of mechanical deformation on guest diffusion in zeolitic imidazolate frameworks

The effect of the elastic strain modes of MOFs on the guest diffusivity was presented and analysed.

Graphical abstract: Impact of mechanical deformation on guest diffusion in zeolitic imidazolate frameworks
Open Access Paper

Compositional control of pore geometry in multivariate metal–organic frameworks: an experimental and computational study

Changing the ratio of the dicarboxylates, L : L′, in MOFs of the general formula [Zn2(L)2–x(L′)x(dabco)] affords control of the pore geometry, through non-covalent interactions between the ligands.

Graphical abstract: Compositional control of pore geometry in multivariate metal–organic frameworks: an experimental and computational study
Paper

Crystal phase competition by addition of a second metal cation in solid solution metal–organic frameworks

Addition of small amounts of a second metal cation results in crystal phase competition during the synthesis of solid-solution MOFs.

Graphical abstract: Crystal phase competition by addition of a second metal cation in solid solution metal–organic frameworks
Open Access Paper

Understanding and solving disorder in the substitution pattern of amino functionalized MIL-47(V)

Electronic energies and elastic constants of four amino functionalized MIL-47(V) supercells were computed using the plane wave density functional theory to determine the influence of the substituent positions on the organic linker.

Graphical abstract: Understanding and solving disorder in the substitution pattern of amino functionalized MIL-47(V)
Paper

High pressure behaviour and elastic properties of a dense inorganic–organic framework

The hydrostatic behaviour of a cubic dense inorganic–organic framework [DABCOH22+][K(ClO4)3] has been systematically studied via high-pressure synchrotron X-ray powder diffraction. Further first principles calculations of full elastic tensors give full mapping of the Young's moduli, shear moduli and Poisson's ratios of this material.

Graphical abstract: High pressure behaviour and elastic properties of a dense inorganic–organic framework
Paper

Exploration of the mechanical behavior of metal organic frameworks UiO-66(Zr) and MIL-125(Ti) and their NH2 functionalized versions

The structural behaviour under mechanical stimuli of two metal organic frameworks, UiO-66(Zr) and MIL-125(Ti) and their amino-functionalized derivatives has been investigated by high-pressure powder X-ray diffraction up to 3.5 GPa.

Graphical abstract: Exploration of the mechanical behavior of metal organic frameworks UiO-66(Zr) and MIL-125(Ti) and their NH2 functionalized versions
Paper

Molecular dynamics simulation study of various zeolitic imidazolate framework structures

We report the results of a series of molecular dynamics simulations on a number of zinc zeolitic imidazolate framework (ZIF) structures together with some lattice dynamics calculations on ZIF-4, providing information about the flexibilities of these structures.

Graphical abstract: Molecular dynamics simulation study of various zeolitic imidazolate framework structures
Paper

Synthesis and stabilization of a hypothetical porous framework based on a classic flexible metal carboxylate cluster

A hypothetical porous network isomeric to MIL-88/MIL-101 has been realized by the introduction of terminal ligands and further stabilized by crosslinking.

Graphical abstract: Synthesis and stabilization of a hypothetical porous framework based on a classic flexible metal carboxylate cluster
Paper

A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling

Amorphization of zeolitic imidazolate frameworks during ball-milling is much more rapid than that of aluminosilicate zeolites.

Graphical abstract: A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling
Paper

Mixed-linker solid solutions of functionalized pillared-layer MOFs – adjusting structural flexibility, gas sorption, and thermal responsiveness

Structural flexibility in pillared-layer metal–organic frameworks can be controlled via the concept of mixed-linker solid solutions.

Graphical abstract: Mixed-linker solid solutions of functionalized pillared-layer MOFs – adjusting structural flexibility, gas sorption, and thermal responsiveness
Paper

A generalized adsorption-phase transition model to describe adsorption rates in flexible metal organic framework RPM3-Zn

The rate of adsorption to a flexible metal-organic framework is described via generalization of the Avrami theory of phase transition kinetics.

Graphical abstract: A generalized adsorption-phase transition model to describe adsorption rates in flexible metal organic framework RPM3-Zn
Paper

Thermodynamics of the structural transition in metal–organic frameworks

A thermodynamic study of the structural large-pore (LP) to narrow pore (NP) transition in various Metal Organic Frameworks (MOFs) is presented.

Graphical abstract: Thermodynamics of the structural transition in metal–organic frameworks
Paper

Understanding gate adsorption behaviour of CO2 on elastic layer-structured metal–organic framework-11

We demonstrate that CO2 gate adsorption behaviour of elastic layer-structured metal–organic framework-11 can be described by a thermodynamic model by free energy analysis with the aid of an adsorption experiment and a molecular simulation.

Graphical abstract: Understanding gate adsorption behaviour of CO2 on elastic layer-structured metal–organic framework-11
Paper

Exact matrix treatment of an osmotic ensemble model of adsorption and pressure induced structural transitions in metal organic frameworks

Here we present an exactly treated quasi-one dimensional statistical mechanical osmotic ensemble model of pressure and adsorption induced breathing structural transformations of metal–organic frameworks (MOFs).

Graphical abstract: Exact matrix treatment of an osmotic ensemble model of adsorption and pressure induced structural transitions in metal organic frameworks
Paper

The cation-dependent structural phase transition and dielectric response in a family of cyano-bridged perovskite-like coordination polymers

The cation-dependent phase transition and the relevant dielectric response were demonstrated in a family of cyano-bridged perovskite-like coordination polymers, [(CH3)nNH4−n]2[KFe(CN)6] (n = 1–4).

Graphical abstract: The cation-dependent structural phase transition and dielectric response in a family of cyano-bridged perovskite-like coordination polymers
Open Access Paper

Structure and properties of Al-MIL-53-ADP, a breathing MOF based on the aliphatic linker molecule adipic acid

A new breathing Al-MIL-53 framework incorporating adipic acid as linker molecules is reported and characterised in detail.

Graphical abstract: Structure and properties of Al-MIL-53-ADP, a breathing MOF based on the aliphatic linker molecule adipic acid
Paper

The guest-dependent thermal response of the flexible MOF Zn2(BDC)2(DABCO)

The flexible MOF, Zn2(BDC)2(DABCO) presents unusual guest-dependent structural responses upon temperature changes.

Graphical abstract: The guest-dependent thermal response of the flexible MOF Zn2(BDC)2(DABCO)
Paper

Encapsulation of dyes in metal–organic frameworks and their tunable nonlinear optical properties

Two series of cationic dyes have been encapsulated in the 1D channel of MOFs, and the tunable second order nonlinear optical properties of these MOF⊃dye materials were observed.

Graphical abstract: Encapsulation of dyes in metal–organic frameworks and their tunable nonlinear optical properties
Open Access Paper

Molecular simulation of low temperature argon adsorption in several models of IRMOF-1 with defects and structural disorder

Low temperature adsorption of argon in several conceptual models of IRMOF-1 featuring various types of defects and inclusions has been investigated.

Graphical abstract: Molecular simulation of low temperature argon adsorption in several models of IRMOF-1 with defects and structural disorder
Paper

Compositional dependence of anomalous thermal expansion in perovskite-like ABX3 formates

Thermal expansion in ABX3 formates is correlated to the size and molecular anisotropy of the A- and B-site cations.

Graphical abstract: Compositional dependence of anomalous thermal expansion in perovskite-like ABX3 formates
Paper

The flexibility of modified-linker MIL-53 materials

The flexibility of eight aluminium hydroxo terephthalates [Al(OH)(BDC–X)] (X = –H, –CH3, –Cl, –Br, –NH2, –NO2, –(OH)2, –CO2H) has been investigated upon thermal dehydration, superhydration and methanol adsorption/desorption using in situ powder X-ray diffraction.

Graphical abstract: The flexibility of modified-linker MIL-53 materials
Paper

Explaining the mechanical mechanisms of zeolitic metal–organic frameworks: revealing auxeticity and anomalous elasticity

The detailed mechanical characteristics of four structurally polymorphic ZIFs have been computed using density functional theory. We elucidate the anomalous elastic behaviour ranging from zero Poisson's ratio and auxeticity, to negative linear compressibility and a remarkably low resistance to shear deformation.

Graphical abstract: Explaining the mechanical mechanisms of zeolitic metal–organic frameworks: revealing auxeticity and anomalous elasticity
Paper

High volumetric uptake of ammonia using Cu-MOF-74/Cu-CPO-27

The MOF Cu-MOF-74/Cu-CPO-27 was identified as a candidate for high-volumetric ammonia uptake due to the high density of Cu sites.

Graphical abstract: High volumetric uptake of ammonia using Cu-MOF-74/Cu-CPO-27
Paper

Elucidating the mechanism responsible for anomalous thermal expansion in a metal–organic framework

A mechanistic model is developed to reproduce concerted changes in the internal coordinates of the coordination helix of a MOF and evaluated using DFT.

Graphical abstract: Elucidating the mechanism responsible for anomalous thermal expansion in a metal–organic framework
43 items

About this collection

Guest edited by: Professor Anthony Cheetham FRS, Professor Alain Fuchs FRSC, Dr Thomas Bennett and Dr François-Xavier Coudert.

This themed issue focuses on the experimental characterization, fundamental understanding and computational modelling of the flexibility and/or disorder of metal–organic frameworks (MOFs), and other inorganic framework-type materials. It also encompasses the consequences of this flexibility for the proposed applications of MOFs, and the associated possibilities to leverage these properties to design novel materials with targeted properties.

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