Heterogeneous Postassembly Modification of Zirconium Metal-Organic Cages in Supramolecular Frameworks

2021 ◽  
Author(s):  
Guoliang Liu ◽  
Ziqi Yang ◽  
Mi Zhou ◽  
Yuxiang Wang ◽  
Daqiang Yuan ◽  
...  
Keyword(s):  
Functional Groups ◽  
Self Assembly ◽  
Metal Organic ◽  
Zirconium Metal

We report a heterogeneous postassembly modification (PAM) to synthesize a zirconium metal-organic cage decorated with acrylate functional groups, ZrT-1-AA, which cannot be synthesized by direct coordination-driven self-assembly owing to the...

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.

scholarly journals In situ self-assembly of zirconium metal–organic frameworks onto ultrathin carbon nitride for enhanced visible light-driven conversion of CO2 to CO

2020 ◽  
Vol 8 (12) ◽  
pp. 6034-6040 ◽  
Author(s):  
Yanan Wang ◽  
Wenlong Zhen ◽  
Yiqing Zeng ◽  
Shipeng Wan ◽  
Haiwei Guo ◽  
...  
Keyword(s):  
Visible Light ◽  
Self Assembly ◽  
Carbon Nitride ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Assembly Method ◽  
Visible Light Driven ◽  
Metal Organic ◽  
Zirconium Metal

A series of Zr-porphyrin metal–organic framework (Zr-PMOF)/ultrathin g-C3N4 (UCN) heterostructure photocatalysts, as stable and efficient catalysts for the photoreduction of CO2, have been fabricated via a facile in situ hydrothermal self-assembly method.

Optimizing zirconium metal–organic frameworks through steric tuning for efficient removal of Cr2O72−

2020 ◽  
Vol 56 (72) ◽  
pp. 10513-10516
Author(s):  
Xiurong Zhang ◽  
Weidong Fan ◽  
Mingyue Fu ◽  
Weifeng Jiang ◽  
Kebin Lu ◽  
...  
Keyword(s):  
Synergistic Effect ◽  
Adsorption Capacity ◽  
Functional Groups ◽  
Metal Organic Frameworks ◽  
Adsorption Rate ◽  
Porous Structures ◽  
Efficient Removal ◽  
Metal Organic ◽  
Zirconium Metal

Three Zr-based MOFs are obtained through steric tuning. The synergistic effect between porous structures and functional groups enhanced the adsorption capacity and adsorption rate for Cr2O72−.

The effect of functional groups in the aqueous-phase selective sensing of Fe(iii) ions by thienothiophene-based zirconium metal–organic frameworks and the design of molecular logic gates

2018 ◽  
Vol 47 (4) ◽  
pp. 1159-1170 ◽  
Author(s):  
Rana Dalapati ◽  
Ülkü Kökçam-Demir ◽  
Christoph Janiak ◽  
Shyam Biswas
Keyword(s):  
Aqueous Medium ◽  
Functional Groups ◽  
Aqueous Phase ◽  
Metal Organic Frameworks ◽  
Logic Gates ◽  
Fluorescence Sensing ◽  
Molecular Logic ◽  
Molecular Logic Gates ◽  
Metal Organic ◽  
Zirconium Metal

The effect of functional groups in the fluorescence sensing of Fe(iii) ions in aqueous medium by four thienothiophene-based Zr MOFs is discussed.

scholarly journals Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage

2021 ◽  
Vol 9 ◽  
Author(s):  
Matthew L. Schneider ◽  
Adrian W. Markwell-Heys ◽  
Oliver M. Linder-Patton ◽  
Witold M. Bloch
Keyword(s):  
Functional Groups ◽  
Self Assembly ◽  
Metal Organic Framework ◽  
The Self ◽  
Porous Solids ◽  
Cross Linking ◽  
Two Dimensional ◽  
Amine Functionalized ◽  
Metal Organic ◽  
Organic Framework

The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry; however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu4L4 lantern cage (1). Importantly, we show control over the coordinative propensity of the exterior amine of the ligand, which enables us to isolate a crystalline, two-dimensional metal-organic framework composed entirely of MOC units (2). Furthermore, we show that the nucleophilicity of the exterior amine of 1 can be accessed in solution to generate a cross-linked cage polymer (3) via imine condensation.

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>

Multiple functional groups in metal–organic frameworks and their positional regioisomerism

2021 ◽  
Vol 438 ◽  
pp. 213892
Author(s):  
Dopil Kim ◽  
Minjung Kang ◽  
Hyeonbin Ha ◽  
Chang Seop Hong ◽  
Min Kim
Keyword(s):  
Functional Groups ◽  
Metal Organic Frameworks ◽  
Metal Organic
Sign in / Sign up

Export Citation Format

Share Document