scholarly journals Adaptive self-assembly and induced-fit transformations of anion-binding metal-organic macrocycles

2017 ◽  
Vol 8 (1) ◽  
Author(s):  
Ting Zhang ◽  
Li-Peng Zhou ◽  
Xiao-Qing Guo ◽  
Li-Xuan Cai ◽  
Qing-Fu Sun
Keyword(s):  
Self Assembly ◽  
Anion Binding ◽  
Induced Fit ◽  
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>

scholarly journals Anion binding in metal-organic frameworks

2021 ◽  
pp. 213708
Author(s):  
Xin Wu ◽  
Lauren K. Macreadie ◽  
Philip A. Gale
Keyword(s):  
Metal Organic Frameworks ◽  
Anion Binding ◽  
Metal Organic

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

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.

Engineering an iridium-containing metal–organic molecular capsule for induced-fit geometrical conversion and dual catalysis

2016 ◽  
Vol 52 (62) ◽  
pp. 9628-9631 ◽  
Author(s):  
Xuezhao Li ◽  
Jinguo Wu ◽  
Liyong Chen ◽  
Xiaoming Zhong ◽  
Cheng He ◽  
...  
Keyword(s):  
Cooperative Binding ◽  
Induced Fit ◽  
Molecular Capsule ◽  
Metal Organic ◽  
Dual Catalysis ◽  
Carbonate Anion

Quantitative dynamic capsule–capsule conversion by cooperative binding one carbonate anion and switchable dual catalysis was achieved within an Ir2Co3-type capsule.

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