Porous Colloidal Hydrogels Formed by Coordination‐Driven Self‐Assembly of Charged Metal‐Organic Polyhedra

2021 ◽  
Author(s):  
Zaoming Wang ◽  
Gavin A. Craig ◽  
Alexandre Legrand ◽  
Frederik Haase ◽  
Saori Minami ◽  
...  
Keyword(s):  
Self Assembly ◽  
Metal Organic

Kinetic Control of Interpenetration in Fe-Biphenyl-4,4′-dicarboxylate MOFs by Coordination and Oxidation Modulation

2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  
Keyword(s):  
Self Assembly ◽  
Surface Areas ◽  
Metal Precursors ◽  
Additional Coordination ◽  
Fine Control ◽  
Multiple Alternative ◽  
Metal Organic ◽  
Dft Simulations ◽  
High Valent ◽  
And Control

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>

Mineralization and Self‐assembly of Gold Nanoparticles using Sulfur Amino Acid Modified Hierarchically Porous Metal‐Organic Frameworks

2021 ◽  
Vol 6 (4) ◽  
pp. 712-716
Author(s):  
Xiao Liu ◽  
Yaoyu Liang ◽  
Jiayu Liu ◽  
Se Shi ◽  
Yuefei Wang ◽  
...  
Keyword(s):  
Gold Nanoparticles ◽  
Amino Acid ◽  
Self Assembly ◽  
Metal Organic Frameworks ◽  
Porous Metal ◽  
Sulfur Amino Acid ◽  
Hierarchically Porous ◽  
Metal Organic

scholarly journals Millimeter-Scale Zn(3-ptz)2 Metal–Organic Framework Single Crystals: Self-Assembly Mechanism and Growth Kinetics

ACS Omega ◽  
2021 ◽  
Author(s):  
Juan M. Garcia-Garfido ◽  
Javier Enríquez ◽  
Ignacio Chi-Durán ◽  
Iván Jara ◽  
Leonardo Vivas ◽  
...  
Keyword(s):  
Single Crystals ◽  
Growth Kinetics ◽  
Self Assembly ◽  
Metal Organic Framework ◽  
Assembly Mechanism ◽  
Metal Organic ◽  
Organic Framework

A ratiometric optical strategy for bromide and iodide ion sensing based on target-induced competitive coordination of a metal–organic nanosystem

2020 ◽  
Vol 8 (33) ◽  
pp. 11517-11524
Author(s):  
Yu Zhu Fan ◽  
Lei Han ◽  
Shi Gang Liu ◽  
Ying Zhang ◽  
Hong Qun Luo ◽  
...  
Keyword(s):  
Self Assembly ◽  
Iodide Ions ◽  
Ratiometric Sensing ◽  
Ion Sensing ◽  
Coordination Bonding ◽  
Iodide Ion ◽  
Competitive Coordination ◽  
Metal Organic

A metal–organic nanosystem constructed via coordination bonding-induced self-assembly is used for fluorescence and scattering ratiometric sensing of bromide and iodide ions.

scholarly journals Mechanochemical and solvent-free assembly of zirconium-based metal–organic frameworks

2016 ◽  
Vol 52 (10) ◽  
pp. 2133-2136 ◽  
Author(s):  
Krunoslav Užarević ◽  
Timothy C. Wang ◽  
Su-Young Moon ◽  
Athena M. Fidelli ◽  
Joseph T. Hupp ◽  
...  
Keyword(s):  
Solid State ◽  
High Temperatures ◽  
Self Assembly ◽  
Metal Organic Frameworks ◽  
Accelerated Aging ◽  
Solvent Free ◽  
Catalytically Active ◽  
Metal Organic ◽  
Strong Acids ◽  
Zirconium Metal

Mechanochemistry and accelerated aging are new routes to zirconium metal–organic frameworks, yielding UiO-66 and catalytically active UiO-66-NH2 accessible on the gram scale through mild solid-state self-assembly, without strong acids, high temperatures or excess reactants.

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