scholarly journals Tuning Binding Tendencies of Small Molecules in Metal–Organic Frameworks with Open Metal Sites by Metal Substitution and Linker Functionalization

2018 ◽  
Vol 122 (48) ◽  
pp. 27486-27494 ◽  
Author(s):  
Wenqin You ◽  
Yang Liu ◽  
Joshua D. Howe ◽  
Dai Tang ◽  
David S. Sholl
Keyword(s):  
Small Molecules ◽  
Metal Organic Frameworks ◽  
Metal Substitution ◽  
Open Metal Sites ◽  
Metal Organic

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>

Small Molecules, Big Effects: Tuning Adsorption and Catalytic Properties of Metal–Organic Frameworks

2021 ◽  
Vol 33 (4) ◽  
pp. 1444-1454
Author(s):  
Xinyao Liu ◽  
Kent O. Kirlikovali ◽  
Zhijie Chen ◽  
Kaikai Ma ◽  
Karam B. Idrees ◽  
...  
Keyword(s):  
Small Molecules ◽  
Catalytic Properties ◽  
Metal Organic Frameworks ◽  
Metal Organic

scholarly journals Innenrücktitelbild: Understanding CO2Dynamics in Metal-Organic Frameworks with Open Metal Sites (Angew. Chem. 16/2013)

2013 ◽  
Vol 125 (16) ◽  
pp. 4589-4589
Author(s):  
Li-Chiang Lin ◽  
Jihan Kim ◽  
Xueqian Kong ◽  
Eric Scott ◽  
Thomas M. McDonald ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Open Metal Sites ◽  
Metal Organic

Adsorption of Small Molecules on Cu3(btc)2 and Cu3–xZnx(btc)2 Metal–Organic Frameworks (MOF) As Studied by Solid-State NMR

2013 ◽  
Vol 117 (15) ◽  
pp. 7703-7712 ◽  
Author(s):  
Farhana Gul-E-Noor ◽  
Matthias Mendt ◽  
Dieter Michel ◽  
Andreas Pöppl ◽  
Harald Krautscheid ◽  
...  
Keyword(s):  
Solid State ◽  
Small Molecules ◽  
Solid State Nmr ◽  
Metal Organic Frameworks ◽  
Metal Organic

scholarly journals Metal–Organic Framework Hybrid Materials and Their Applications

Crystals ◽  
2018 ◽  
Vol 8 (8) ◽  
pp. 325 ◽  
Author(s):  
Joshua Sosa ◽  
Timothy Bennett ◽  
Katherine Nelms ◽  
Brandon Liu ◽  
Roberto Tovar ◽  
...  
Keyword(s):  
Small Molecules ◽  
Hybrid Materials ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Gas Storage ◽  
Superior Performance ◽  
Separation Energy ◽  
New Materials ◽  
Metal Organic ◽  
Covalent Modifications

The inherent porous nature and facile tunability of metal–organic frameworks (MOFs) make them ideal candidates for use in multiple fields. MOF hybrid materials are derived from existing MOFs hybridized with other materials or small molecules using a variety of techniques. This led to superior performance of the new materials by combining the advantages of MOF components and others. In this review, we discuss several hybridization methods for the preparation of various MOF hybrids with representative examples from the literature. These methods include covalent modifications, noncovalent modifications, and using MOFs as templates or precursors. We also review the applications of the MOF hybrids in the fields of catalysis, drug delivery, gas storage and separation, energy storage, sensing, and others.

Flexible luminescent non-lanthanide metal–organic frameworks as small molecules sensors

2021 ◽  
Author(s):  
Sajal Khatua ◽  
Chidharth Krishnaraj ◽  
Debendra Chandra Baruah ◽  
Pascal Van Der Voort ◽  
Himanshu Sekhar Jena
Keyword(s):  
Small Molecules ◽  
Small Molecule ◽  
Metal Organic Frameworks ◽  
Luminescence Properties ◽  
Flexible Structure ◽  
Metal Organic ◽  
Lanthanide Metal

Non-lanthanide metal–organic frameworks with flexible structure and luminescence properties are systematically discussed as potential small molecule sensors.

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