Providing evidence for the requirements to achieve supramolecular materials based on metal–nucleobase entities

CrystEngComm ◽  
2018 ◽  
Vol 20 (18) ◽  
pp. 2528-2539 ◽  
Author(s):  
Jintha Thomas-Gipson ◽  
Garikoitz Beobide ◽  
Oscar Castillo ◽  
Antonio Luque ◽  
Jon Pascual-Colino ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Supramolecular Materials ◽  
Metal Organic

This article evaluates the strategy to design supramolecular metal–organic frameworks using metal–nucleobase entities as building units.

scholarly journals Probing the Mechanochemistry of Metal-Organic Frameworks with Low-Frequency Vibrational Spectroscopy

2018 ◽  
Author(s):  
Wei Zhang ◽  
Jefferson Maul ◽  
Diana Vulpe ◽  
Peyman Z. Moghadam ◽  
David Fairen-jimenez ◽  
...  
Keyword(s):  
Terahertz Spectroscopy ◽  
State Of The Art ◽  
Metal Organic Frameworks ◽  
Low Frequency ◽  
Structural Response ◽  
Vibrational Modes ◽  
Supramolecular Materials ◽  
Metal Organic ◽  
Temperature And Pressure ◽  
External Stimuli

<div>The identification of low-frequency vibrational motions of metal-organic frameworks (MOFs) allows for a full understanding of their mechanical and structural response upon perturbation by external stimuli such as temperature, pressure, and adsorption. Here, we describe the unique combination of an experimental temperature- and pressure-dependent terahertz spectroscopy system with state-of-the-art quantum mechanical simulation to measure and atomistically assign specific low-frequency vibrational modes that directly drive the mechanochemical properties of this important class of porous materials. Our work highlights the complex interplay between structural, vibrational, and mechanochemical phenomena, all of which are key to the effective exploitation of MOFs. We demonstrate the critical importance of terahertz vibrational motions on the function of MOFs, and how this information can be measured and interpreted in a method that can be applied widely to any supramolecular materials. </div><div><br></div>

scholarly journals Probing the Mechanochemistry of Metal-Organic Frameworks with Low-Frequency Vibrational Spectroscopy

2018 ◽  
Author(s):  
Wei Zhang ◽  
Jefferson Maul ◽  
Diana Vulpe ◽  
Peyman Z. Moghadam ◽  
David Fairen-jimenez ◽  
...  
Keyword(s):  
Terahertz Spectroscopy ◽  
State Of The Art ◽  
Metal Organic Frameworks ◽  
Low Frequency ◽  
Structural Response ◽  
Vibrational Modes ◽  
Supramolecular Materials ◽  
Metal Organic ◽  
Temperature And Pressure ◽  
External Stimuli

<div>The identification of low-frequency vibrational motions of metal-organic frameworks (MOFs) allows for a full understanding of their mechanical and structural response upon perturbation by external stimuli such as temperature, pressure, and adsorption. Here, we describe the unique combination of an experimental temperature- and pressure-dependent terahertz spectroscopy system with state-of-the-art quantum mechanical simulation to measure and atomistically assign specific low-frequency vibrational modes that directly drive the mechanochemical properties of this important class of porous materials. Our work highlights the complex interplay between structural, vibrational, and mechanochemical phenomena, all of which are key to the effective exploitation of MOFs. We demonstrate the critical importance of terahertz vibrational motions on the function of MOFs, and how this information can be measured and interpreted in a method that can be applied widely to any supramolecular materials. </div><div><br></div>

Metal-Organic Frameworks

2021 ◽  
Author(s):  
Lars Öhrström ◽  
Francoise M. Amombo Noa
Keyword(s):  
Metal Organic Frameworks ◽  
Metal Organic

Substrate templated synthesis of single-phase and uniform Zr-porphyrin-based metal–organic frameworks

2020 ◽  
Vol 7 (1) ◽  
pp. 221-231
Author(s):  
Seong Won Hong ◽  
Ju Won Paik ◽  
Dongju Seo ◽  
Jae-Min Oh ◽  
Young Kyu Jeong ◽  
...  
Keyword(s):  
Chemical Bath Deposition ◽  
Single Phase ◽  
Metal Organic Frameworks ◽  
Templated Synthesis ◽  
Pore Structures ◽  
Phase Pure ◽  
Metal Organic ◽  
Cbd Method

We successfully demonstrate that the chemical bath deposition (CBD) method is a versatile method for synthesizing phase-pure and uniform MOFs by controlling their nucleation stages and pore structures.

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

2019 ◽  
Author(s):  
Andrew Rosen ◽  
M. Rasel Mian ◽  
Timur Islamoglu ◽  
Haoyuan Chen ◽  
Omar Farha ◽  
...  
Keyword(s):  
Density Functional ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Screening Methods ◽  
Bridging Ligands ◽  
Metal Centers ◽  
Computational Screening ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Unsaturated Metal Sites

<p>Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O<sub>2</sub> and N<sub>2</sub> adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br<sup>-</sup>, μ-Cl<sup>-</sup>, μ-F<sup>-</sup>, μ-SH<sup>-</sup>, or μ-OH<sup>-</sup> groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O<sub>2</sub> affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O<sub>2</sub>. In contrast with O<sub>2</sub> adsorption, N<sub>2</sub> adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V<sup>2+</sup> open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl<sup>-</sup> ligands of M<sub>2</sub>Cl<sub>2</sub>(BBTA) (H<sub>2</sub>BBTA = 1<i>H</i>,5<i>H</i>-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH<sup>-</sup> groups would significantly enhance the strength of O<sub>2</sub> adsorption at the open metal sites without a corresponding increase in the N<sub>2</sub> affinity. Experimental investigation of Co<sub>2</sub>Cl<sub>2</sub>(BBTA) and Co<sub>2</sub>(OH)<sub>2</sub>(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O<sub>2</sub> at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH<sup>-</sup><sub> </sub>ligands and the presence of H-bonding interactions between the μ-OH<sup>-</sup> bridging ligands and the O<sub>2</sub> adsorbate.</p>

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