Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal–Organic Frameworks

2008 ◽  
Vol 14 (8) ◽  
pp. 2389-2397 ◽  
Author(s):  
Pascal D. C. Dietzel ◽  
Rune E. Johnsen ◽  
Richard Blom ◽  
Helmer Fjellvåg
Keyword(s):  
Structural Changes ◽  
Metal Organic Frameworks ◽  
Metal Atoms ◽  
Metal Organic

Long and local range structural changes in M[(bdc)(ted)0.5] (M = Zn, Ni or Cu) metal organic frameworks upon spontaneous thermal dispersion of LiCl and adsorption of carbon dioxide

2015 ◽  
Vol 212 ◽  
pp. 8-17 ◽  
Author(s):  
Jennifer Guerrero-Medina ◽  
Génesis Mass-González ◽  
Leonardo Pacheco-Londoño ◽  
Samuel P. Hernández-Rivera ◽  
Riqiang Fu ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Structural Changes ◽  
Metal Organic Frameworks ◽  
Thermal Dispersion ◽  
Metal Organic ◽  
Local Range

Tuning Packing, Structural Flexibility, and Porosity in 2D Metal–Organic Frameworks by Metal Node Choice

2019 ◽  
Vol 72 (10) ◽  
pp. 797 ◽  
Author(s):  
Witold M. Bloch ◽  
Christian J. Doonan ◽  
Christopher J. Sumby
Keyword(s):  
Structural Changes ◽  
Metal Organic Frameworks ◽  
Chemical Properties ◽  
Complete Removal ◽  
Structural Flexibility ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
Metal Organic ◽  
Physical And Chemical ◽  
And Chemical Properties

Understanding the key features that determine structural flexibility in metal–organic frameworks (MOFs) is key to exploiting their dynamic physical and chemical properties. We have previously reported a 2D MOF material, CuL1, comprising five-coordinate metal nodes that displays exceptional CO2/N2 selectively (L1=bis(4-(4-carboxyphenyl)-1H-pyrazolyl)methane). Here we examine the effect of utilising six-coordinate metal centres (CoII and NiII) in the synthesis of isostructural MOFs from L1, namely CoL1 and NiL1. The octahedral geometry of the metal centre within the MOF analogues precludes an ideal eclipse of the 2D layers, resulting in an offset stacking, and in certain cases, the formation of 2-fold interpenetrated analogues β-CoL1 and β-NiL1. We used a combination of thermogravimetric analysis (TGA), and powder and single crystal X-ray diffraction (PXRD and SCXRD) to show that desolvation is accompanied by a structural change for NiL1, and complete removal of the coordinated H2O ligands results in a reduction in long-range order. The offset nature of the 2D layers in combination with the structural changes impedes the adsorption of meaningful quantities of gases (N2, CO2), highlighting the importance of a five-coordinate metal centre in achieving optimal pore accessibility for this family of flexible materials.

Stimuli-responsive structural changes in metal–organic frameworks

2020 ◽  
Vol 56 (66) ◽  
pp. 9416-9432 ◽  
Author(s):  
Zhanning Liu ◽  
Lu Zhang ◽  
Daofeng Sun
Keyword(s):  
Structural Changes ◽  
Metal Organic Frameworks ◽  
Stimuli Responsive ◽  
Feature Article ◽  
Metal Organic ◽  
External Stimuli

This feature article mainly summarizes how the structure of MOFs changes under external stimuli.

scholarly journals New insights into solvent-induced structural changes of 13C labelled metal–organic frameworks by solid state NMR

2019 ◽  
Vol 55 (62) ◽  
pp. 9140-9143 ◽  
Author(s):  
Marcus Rauche ◽  
Sebastian Ehrling ◽  
Simon Krause ◽  
Irena Senkovska ◽  
Stefan Kaskel ◽  
...  
Keyword(s):  
Solid State Nmr ◽  
Structural Changes ◽  
Metal Organic Frameworks ◽  
Site Specific ◽  
Isotope Labelling ◽  
Specific Host ◽  
Depth Analysis ◽  
Adsorption Complexes ◽  
Metal Organic ◽  
Labelling Scheme

The proposed 13C isotope-labelling scheme enables the in-depth analysis of site-specific host–guest interactions and adsorption complexes formed in MOFs.

scholarly journals Integration of Fluorescent Functionality into Pressure Amplifying Metal-Organic Frameworks

2021 ◽  
Author(s):  
Francesco Walenszus ◽  
Jack D. Evans ◽  
Volodymyr Bon ◽  
Friedrich Schwotzer ◽  
Irena Senkovska ◽  
...  
Keyword(s):  
Structural Changes ◽  
Gas Adsorption ◽  
Metal Organic Frameworks ◽  
Metal Exchange ◽  
Limited Information ◽  
X Ray Diffraction ◽  
Metal Organic ◽  
Synthetic Metal ◽  
External Stimuli ◽  
Highly Porous

The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal-organic frameworks. In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption and pressure amplification is one of the more recent discoveries in this field, initially observed in the cubic DUT-49 framework. In recent years the structural contraction was monitored by physisorption, X‑ray diffraction, NMR and EPR techniques, providing only limited information about the electronic structure of the ligand. In this work we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT‑140(M) (M - Cu, Co, Zn) crystalizing in space group. DUT‑140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m2g-1 and a pore volume of 2.59 cm3g-1. Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using post-synthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu) spectroscopic and computational methods were used to study the light absorption properties.

Structure and properties of dynamic metal–organic frameworks: a brief accounts of crystalline-to-crystalline and crystalline-to-amorphous transformations

CrystEngComm ◽  
2018 ◽  
Vol 20 (10) ◽  
pp. 1322-1345 ◽  
Author(s):  
Arijit Halder ◽  
Debajyoti Ghoshal
Keyword(s):  
Structural Changes ◽  
Metal Organic Frameworks ◽  
Structure And Properties ◽  
Metal Organic ◽  
External Stimuli

External stimuli-driven structural changes and the associated properties of dynamic MOFs are discussed with examples.

scholarly journals Development of Phosphonate Monoesters Building Units in Metal-Organic Frameworks

2014 ◽  
Vol 70 (a1) ◽  
pp. C1127-C1127
Author(s):  
Benjamin Gelfand ◽  
Jian-Bin Lin ◽  
George Shimizu
Keyword(s):  
Metal Organic Frameworks ◽  
Design Strategy ◽  
Layered Material ◽  
Water Stability ◽  
New Materials ◽  
Isopropyl Esters ◽  
Porous Framework ◽  
Metal Atoms ◽  
Metal Organic ◽  
Ester Moiety

The use of predictable coordination geometries and the development of new ligands has allowed supramolecular chemists to design a plethora of new materials. Among these are metal-organic frameworks (MOFs), which are composed of ligands coordinating to metal atoms or clusters to generate a framework with potential porosity. MOFs exemplify supramolecular design strategy as their extended structure and tunable properties allow them to be applied for various applications.1 To date, many MOFs utilize carboxylates as the coordinating group since they have well studied coordination geometries and thus predictable framework topologies. Though there are examples of carboxylate-based MOFs possessing water stability, most do not possess this key feature, hindering their application in industrial settings. Phosphonate monoesters (PMEs) have been investigated as a means to impart water stability to a MOF by kinetically shielding the linker-metal bond with the ester moiety.2 Unfortunately, phosphonate monoesters have relatively unexplored coordination geometries, with most studies focusing on chlodronic acid and its derivatives, which do not typically form porous materials. In an attempt to establish building units based on PMEs, 1,4-benzenediphosphonate monoester ligands have been synthesized, coordinated to Cu(II), and characterized. It was found that while the methyl and ethyl analogues form similar 3-D structures with poor water stability,3 the isopropyl analogue forms a layered material possessing water stability. The isopropyl analogue contains chains of Cu-PME, with the isopropyl esters lying directly above and below the Cu atoms, kinetically shielding this bond from water. This water stable building unit was predicted to generate a porous framework with non-linear ligands. To test this hypothesis, 1,3,5-benzenetriphosphonate monoisopropyl ester was synthesized and coordinated to Cu(II). Unfortunately, no single crystal of sufficient quality has been produced, though a predicted and refined structure matches well to various characterization techniques. As predicted, this material is porous and does not degrade in harsh humid conditions (353K and 90% relative humidity).

scholarly journals Integration of Fluorescent Functionality into Pressure Amplifying Metal-Organic Frameworks

2021 ◽  
Author(s):  
Francesco Walenszus ◽  
Jack D. Evans ◽  
Volodymyr Bon ◽  
Friedrich Schwotzer ◽  
Irena Senkovska ◽  
...  
Keyword(s):  
Structural Changes ◽  
Gas Adsorption ◽  
Metal Organic Frameworks ◽  
Metal Exchange ◽  
Limited Information ◽  
X Ray Diffraction ◽  
Metal Organic ◽  
Synthetic Metal ◽  
External Stimuli ◽  
Highly Porous

The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal-organic frameworks. In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption and pressure amplification is one of the more recent discoveries in this field, initially observed in the cubic DUT-49 framework. In recent years the structural contraction was monitored by physisorption, X‑ray diffraction, NMR and EPR techniques, providing only limited information about the electronic structure of the ligand. In this work we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT‑140(M) (M - Cu, Co, Zn) crystalizing in space group. DUT‑140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m2g-1 and a pore volume of 2.59 cm3g-1. Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using post-synthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu) spectroscopic and computational methods were used to study the light absorption properties.

scholarly journals Functionalised metal–organic frameworks: a novel approach to stabilising single metal atoms

2017 ◽  
Vol 5 (30) ◽  
pp. 15559-15566 ◽  
Author(s):  
P. Á. Szilágyi ◽  
D. M. Rogers ◽  
I. Zaiser ◽  
E. Callini ◽  
S. Turner ◽  
...  
Keyword(s):  
Transition Metals ◽  
Metal Organic Frameworks ◽  
Model System ◽  
Single Atoms ◽  
Metal Atoms ◽  
Novel Approach ◽  
Metal Organic

We have investigated the potential of metal–organic frameworks for immobilising single atoms of transition metals using a model system of Pd supported on NH2-MIL-101(Cr).

Solvent triggering structural changes for two terbium-based metal–organic frameworks and their photoluminescence sensing

2020 ◽  
Vol 56 (31) ◽  
pp. 4320-4323 ◽  
Author(s):  
Dan Yue ◽  
Yanyan Wang ◽  
Dong Chen ◽  
Zhenling Wang
Keyword(s):  
Structural Changes ◽  
Metal Organic Frameworks ◽  
Luminescence Properties ◽  
Metal Organic

TbPDBA-8 and TbPDBA-9 have been obtained based on the same ligand, and have different structures and luminescence properties.

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