scholarly journals Crystallographic characterization of the metal–organic framework Fe2(bdp)3 upon reductive cation insertion

2020 ◽  
Vol 11 (34) ◽  
pp. 9173-9180 ◽  
Author(s):  
Naomi Biggins ◽  
Michael E. Ziebel ◽  
Miguel I. Gonzalez ◽  
Jeffrey R. Long
Keyword(s):  
Single Crystal ◽  
Gas Adsorption ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Adsorption Properties ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
Organic Framework

Single-crystal X-ray diffraction reveals structural influences on gas adsorption properties in anionic metal–organic frameworks.

scholarly journals Crystallographic Characterization of the Metal–Organic Framework Fe2(bdp)3 upon Reductive Cation Insertion*

2020 ◽  
Author(s):  
Naomi Biggins ◽  
Michael Ziebel ◽  
Miguel Gonzalez ◽  
Jeffrey R. Long
Keyword(s):  
Single Crystal ◽  
Single Crystals ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Π Interactions ◽  
Cation Framework ◽  
Metal Organic ◽  
Organic Framework

<div><p>Precisely locating extra-framework cations in anionic metal–organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure-performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal–organic framework Fe<sub>2</sub>(bdp)<sub>3</sub> (bdp<sup>2−</sup> = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A<sub>2</sub>Fe<sub>2</sub>(bdp)<sub>3</sub>∙<i>y</i>THF<sub> </sub>(A = Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation–π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na<sub>0.5</sub>Fe<sub>2</sub>(bdp)<sub>3 </sub>and Li<sub>2</sub>Fe<sub>2</sub>(bdp)<sub>3</sub> and the first structural characterization of activated metal–organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation­–π interactions. Hydrogen adsorption data indicate that these cation-framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe<sub>2</sub>(bdp)<sub>3</sub>. In contrast, Mg<sub>0.85</sub>Fe<sub>2</sub>(bdp)<sub>3</sub> exhibits enhanced H<sub>2</sub> affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation–framework interactions and thereby promotes stronger cation–H<sub>2</sub> interactions.</p></div>

scholarly journals Crystallographic Characterization of the Metal–Organic Framework Fe2(bdp)3 upon Reductive Cation Insertion*

2020 ◽  
Author(s):  
Naomi Biggins ◽  
Michael Ziebel ◽  
Miguel Gonzalez ◽  
Jeffrey R. Long
Keyword(s):  
Single Crystal ◽  
Single Crystals ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Π Interactions ◽  
Cation Framework ◽  
Metal Organic ◽  
Organic Framework

<div><p>Precisely locating extra-framework cations in anionic metal–organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure-performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal–organic framework Fe<sub>2</sub>(bdp)<sub>3</sub> (bdp<sup>2−</sup> = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A<sub>2</sub>Fe<sub>2</sub>(bdp)<sub>3</sub>∙<i>y</i>THF<sub> </sub>(A = Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation–π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na<sub>0.5</sub>Fe<sub>2</sub>(bdp)<sub>3 </sub>and Li<sub>2</sub>Fe<sub>2</sub>(bdp)<sub>3</sub> and the first structural characterization of activated metal–organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation­–π interactions. Hydrogen adsorption data indicate that these cation-framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe<sub>2</sub>(bdp)<sub>3</sub>. In contrast, Mg<sub>0.85</sub>Fe<sub>2</sub>(bdp)<sub>3</sub> exhibits enhanced H<sub>2</sub> affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation–framework interactions and thereby promotes stronger cation–H<sub>2</sub> interactions.</p></div>

scholarly journals Structural characterization of framework–gas interactions in the metal–organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction

2017 ◽  
Vol 8 (6) ◽  
pp. 4387-4398 ◽  
Author(s):  
Miguel I. Gonzalez ◽  
Jarad A. Mason ◽  
Eric D. Bloch ◽  
Simon J. Teat ◽  
Kevin J. Gagnon ◽  
...  
Keyword(s):  
Single Crystal ◽  
Structural Characterization ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
Gas Interactions ◽  
Organic Framework

In situ single-crystal X-ray diffraction experiments enable the direct observation of weak metal–gas interactions in a metal–organic framework.

Single Crystal X-ray Diffraction Studies of Carbon Dioxide and Fuel-Related Gases Adsorbed on the Small Pore Scandium Terephthalate Metal Organic Framework, Sc2(O2CC6H4CO2)3

Langmuir ◽  
2009 ◽  
Vol 25 (6) ◽  
pp. 3618-3626 ◽  
Author(s):  
Stuart R. Miller ◽  
Paul A. Wright ◽  
Thomas Devic ◽  
Christian Serre ◽  
Gérard Férey ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Single Crystal ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Small Pore ◽  
Metal Organic ◽  
Organic Framework

A Mn(II) Metal-Organic Framework Constructed from a Tetrahedral Silicon-Cored Ligand

2013 ◽  
Vol 275-277 ◽  
pp. 2367-2370
Author(s):  
Qing Yu Ma ◽  
Rui Fang Guan ◽  
Guo Zhong Li ◽  
Deng Xu Wang
Keyword(s):  
Single Crystal ◽  
Metal Organic Framework ◽  
Diffusion Method ◽  
X Ray Diffraction ◽  
X Ray ◽  
Slow Diffusion ◽  
Sheet Structure ◽  
Metal Organic ◽  
1D Chains ◽  
Organic Framework

A novel metal-organic framework, MnCl2(BIPS)2•2CH3OH•2H2O (1) were synthesized from MnCl2 and a tetrahedral silicon-cored ligand, Me2Si(p-C6H4-imdazol-1-yl)2 (BIPS) under the slow diffusion method. The structure was determined by single-crystal X-ray diffraction. Complex 1 is a 2D sheet structure constructed from 1D chains with 34-atom metallamacrocycles.

scholarly journals Single crystal structure and photocatalytic behavior of grafted uranyl on the Zr-node of a pyrene-based metal–organic framework

CrystEngComm ◽  
2020 ◽  
Vol 22 (11) ◽  
pp. 2097-2102 ◽  
Author(s):  
Julia G. Knapp ◽  
Xuan Zhang ◽  
Tatyana Elkin ◽  
Laura E. Wolfsberg ◽  
Sylvia L. Hanna ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Metal Organic Framework ◽  
Uranyl Ion ◽  
Single Crystal Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Photo Oxidation ◽  
Metal Organic ◽  
Organic Framework

The zirconium MOF NU-1000 was post-synthetically modified through solvothermal deposition to include the uranyl ion and characterized via single-crystal X-ray diffraction; photo-oxidation was also performed.

A zinc(II) metal–organic framework with a novel topology formed from 4,4′,4′′-nitrilotribenzoate and 4,4′-bipyridine ligands

2015 ◽  
Vol 71 (9) ◽  
pp. 799-803 ◽  
Author(s):  
Meng Zhao ◽  
Jian Su ◽  
Jun Zhang ◽  
Jie-Ying Wu ◽  
Yu-Peng Tian
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Solvothermal Method ◽  
Metal Organic Framework ◽  
Topological Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Paddle Wheel ◽  
Metal Organic ◽  
Organic Framework

A metal–organic framework with a novel topology, poly[sesqui(μ2-4,4′-bipyridine)bis(dimethylformamide)bis(μ4-4,4′,4′′-nitrilotribenzoato)trizinc(II)], [Zn3(C21H12NO6)2(C10H8N2)1.5(C3H7NO)2]n, was obtained by the solvothermal method using 4,4′,4′′-nitrilotribenzoic acid and 4,4′-bipyridine (bipy). The structure, determined by single-crystal X-ray diffraction analysis, possesses three kinds of crystallographically independent ZnIIcations, as well as binuclear Zn2(COO)4(bipy)2paddle-wheel clusters, and can be reduced to a novel topology of a (3,3,6)-connected 3-nodal net, with the Schläfli symbol {5.62}4{52.6}4{58.87} according to the topological analysis.

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