Enhanced CO2Adsorption in Metal-Organic Frameworks via Occupation of Open-Metal Sites by Coordinated Water Molecules

2009 ◽  
Vol 21 (8) ◽  
pp. 1425-1430 ◽  
Author(s):  
A. Özgür Yazaydın ◽  
Annabelle I. Benin ◽  
Syed A. Faheem ◽  
Paulina Jakubczak ◽  
John J. Low ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Water Molecules ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Coordinated Water

Coordinated Water as New Binding Sites for the Separation of Light Hydrocarbons in Metal–Organic Frameworks with Open Metal Sites

2020 ◽  
Vol 12 (8) ◽  
pp. 9448-9456 ◽  
Author(s):  
Pia Vervoorts ◽  
Andreas Schneemann ◽  
Inke Hante ◽  
Jenny Pirillo ◽  
Yuh Hijikata ◽  
...  
Keyword(s):  
Binding Sites ◽  
Metal Organic Frameworks ◽  
Light Hydrocarbons ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Coordinated Water

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>

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

Synthesis, crystal structure, and quantum mechanical studies regarding a new metal–organic complex based on Cd (II)

2021 ◽  
Author(s):  
zohreh razmara ◽  
Fereshteh Shiri ◽  
Pouya Karimi ◽  
Marek Necas
Keyword(s):  
Three Dimensional ◽  
Pentagonal Bipyramid ◽  
Quantum Mechanical ◽  
Water Molecules ◽  
Organic Complex ◽  
Polymeric Networks ◽  
Metal Organic Complex ◽  
Metal Organic ◽  
Coordinated Water ◽  
Mechanical Studies

Abstract A novel metal-organic complex formulated as [Cd (phen)(dipic) (H2O)2]. 3 H2O (phen = 1, 10-phenanthroline; dipic2−= pyridine-2,6-dicarboxylate) has been hydrothermally synthesized at 150°C for 48h. The structure of Cd complex was characterized by elemental analysis, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and single-crystal X-ray diffraction (SC-XRD). The crystal system of Cd complex is monoclinic with space group C 2/c. The pentagonal bipyramid (seven coordinate) around Cd2+ center filled by two terminal water ligands, one 1,10-phenanthroline, and one pyridine-2,6-dicarboxylate anion. Extensive O–H···O hydrogen bonding interactions involving all coordinated water molecules, dipicolinate oxygens, and crystallization water molecules further stabilize the complex units by linking them to form three-dimensional polymeric networks. Indeed, quantum mechanical studies were performed to understand effective factors on stability of the Cd(II) complex.

scholarly journals Crystal Structure Dependence of the Energy Transfer from Tb(III) to Yb(III) in Metal–Organic Frameworks Based in Bispyrazolylpyridines

Crystals ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 69 ◽  
Author(s):  
Paloma Martinez-Martin ◽  
Josefina Perles ◽  
Juan Carlos Rodriguez-Ubis
Keyword(s):  
Crystal Structure ◽  
Energy Transfer ◽  
Organic Molecules ◽  
Metal Organic Frameworks ◽  
Structure Dependence ◽  
Characteristic Emission ◽  
Metal Organic ◽  
Lanthanide Metal ◽  
Coordinated Water ◽  
Luminescent Behavior

Luminescent mixed lanthanide metal−organic framwork (MOF) materials have been prepared from two polyheterocyclic diacid ligands, 2,6-bis(3-carboxy-1-pyrazolyl)pyridine and 2,6-bis(4-carboxy-1-pyrazolyl)pyridine. The crystal structures of the two organic molecules are presented together with the structures for the MOFs obtained by hydrothermal synthesis either with Yb(III) or mixed Tb(III)/Yb(III) ions. Different coordination architectures result from each ligand, revealing also important differences between the lanthanides. The mixed lanthanide metal−organic frameworks also present diverse luminescent behavior; in the case of 2,6-bis(4-carboxy-1-pyrazolyl)pyridine, where no coordinated water is present in the metal environment, Tb(III) and Yb(III) characteristic emission is observed by excitation of the bispyrazolylpyridine chromophore.

Using Site Heterogeneity in Metal–Organic Frameworks with Bimetallic Open Metal Sites for Olefin/Paraffin Separations

2020 ◽  
Vol 3 (6) ◽  
pp. 5291-5300
Author(s):  
Wenqin You ◽  
Trisha Sen ◽  
Yoshiaki Kawajiri ◽  
Matthew J. Realff ◽  
David S. Sholl
Keyword(s):  
Metal Organic Frameworks ◽  
Open Metal Sites ◽  
Site Heterogeneity ◽  
Metal Organic

scholarly journals Retrofitting metal-organic frameworks

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Christian Schneider ◽  
David Bodesheim ◽  
Julian Keupp ◽  
Rochus Schmid ◽  
Gregor Kieslich
Keyword(s):  
Thermal Expansion ◽  
Low Cost ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Computational Framework ◽  
Expansion Behavior ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Set Up ◽  
Linker Molecules

Abstract The post-synthetic installation of linker molecules between open-metal sites (OMSs) and undercoordinated metal-nodes in a metal-organic framework (MOF) — retrofitting — has recently been discovered as a powerful tool to manipulate macroscopic properties such as the mechanical robustness and the thermal expansion behavior. So far, the choice of cross linkers (CLs) that are used in retrofitting experiments is based on qualitative considerations. Here, we present a low-cost computational framework that provides experimentalists with a tool for evaluating various CLs for retrofitting a given MOF system with OMSs. After applying our approach to the prototypical system CL@Cu3BTC2 (BTC = 1,3,5-benzentricarboxylate) the methodology was expanded to NOTT-100 and NOTT-101 MOFs, identifying several promising CLs for future CL@NOTT-100 and CL@NOTT-101 retrofitting experiments. The developed model is easily adaptable to other MOFs with OMSs and is set-up to be used by experimentalists, providing a guideline for the synthesis of new retrofitted MOFs with modified physicochemical properties.

scholarly journals Modeling Adsorption in Metal–Organic Frameworks with Open Metal Sites: Propane/Propylene Separations

Langmuir ◽  
2012 ◽  
Vol 28 (22) ◽  
pp. 8537-8549 ◽  
Author(s):  
Michael Fischer ◽  
José R. B. Gomes ◽  
Michael Fröba ◽  
Miguel Jorge
Keyword(s):  
Metal Organic Frameworks ◽  
Open Metal Sites ◽  
Metal Organic
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