scholarly journals Methyl-rotation dynamics in metal–organic frameworks probed with terahertz spectroscopy

2018 ◽  
Vol 54 (45) ◽  
pp. 5776-5779 ◽  
Author(s):  
Qi Li ◽  
Adam J. Zaczek ◽  
Timothy M. Korter ◽  
J. Axel Zeitler ◽  
Michael T. Ruggiero
Keyword(s):  
Terahertz Spectroscopy ◽  
Metal Organic Frameworks ◽  
Methyl Groups ◽  
Cryogenic Temperatures ◽  
Void Space ◽  
Metal Organic ◽  
Methyl Rotation ◽  
Rotation Dynamics

In ZIF-8 and its cobalt analogue ZIF-67, the imidazolate methyl-groups, which point directly into the void space, have been shown to freely rotate – even down to cryogenic temperatures.

Quantum Mechanical Interpretation of the Ultra-Low Energy Methyl-Rotation Dynamics in Porous Metal-Organic Frameworks Probed by Low-Frequency Vibrational Spectroscopy and ab initio Simulations

2018 ◽  
Author(s):  
Qi Li ◽  
Adam J. Zaczek ◽  
Timothy M. Korter ◽  
J. Axel Zeitler ◽  
Michael T. Ruggiero
Keyword(s):  
Ab Initio ◽  
Metal Organic Frameworks ◽  
Low Frequency ◽  
Rotor Dynamics ◽  
Quantum Mechanical ◽  
Valuable Insight ◽  
Void Space ◽  
Ab Initio Simulations ◽  
Metal Organic ◽  
Insight Into

<div>Understanding the nature of the interatomic interactions present within the pores of metal-organic frameworks</div><div>is critical in order to design and utilize advanced materials</div><div>with desirable applications. In ZIF-8 and its cobalt analogue</div><div>ZIF-67, the imidazolate methyl-groups, which point directly</div><div>into the void space, have been shown to freely rotate - even</div><div>down to cryogenic temperatures. Using a combination of ex-</div><div>perimental terahertz time-domain spectroscopy, low-frequency</div><div>Raman spectroscopy, and state-of-the-art ab initio simulations,</div><div>the methyl-rotor dynamics in ZIF-8 and ZIF-67 are fully charac-</div><div>terized within the context of a quantum-mechanical hindered-</div><div>rotor model. The results lend insight into the fundamental</div><div>origins of the experimentally observed methyl-rotor dynamics,</div><div>and provide valuable insight into the nature of the weak inter-</div><div>actions present within this important class of materials.</div>

Void Space vs. Surface Functionalization for Proton Conduction in Metal–Organic Frameworks

2021 ◽  
Author(s):  
Marvin K Sarango-Ramírez ◽  
Junkil Park ◽  
Jihan Kim ◽  
Yukihiro Yoshida ◽  
Dae-Woon Lim ◽  
...  
Keyword(s):  
Surface Functionalization ◽  
Metal Organic Frameworks ◽  
Proton Conduction ◽  
Void Space ◽  
Metal Organic

scholarly journals X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

2017 ◽  
Vol 375 (2084) ◽  
pp. 20160028 ◽  
Author(s):  
Michael T. Huxley ◽  
Campbell J. Coghlan ◽  
Witold M. Bloch ◽  
Alexandre Burgun ◽  
Christian J. Doonan ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Metal Organic Frameworks ◽  
Void Space ◽  
X Ray ◽  
X Ray Crystallography ◽  
Metal Nitrates ◽  
Metal Organic

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

scholarly journals Pore environment engineering in metal–organic frameworks for efficient ethane/ethylene separation

2019 ◽  
Vol 7 (22) ◽  
pp. 13585-13590 ◽  
Author(s):  
Xun Wang ◽  
Zheng Niu ◽  
Abdullah M. Al-Enizi ◽  
Ayman Nafady ◽  
Yufang Wu ◽  
...  
Keyword(s):  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Methyl Groups ◽  
Separation Performance ◽  
Metal Organic ◽  
Organic Framework

Methyl groups are introduced on the pore walls of a metal–organic framework to enhance the separation performance of C2H6/C2H4.

Void Space vs. Surface Functionalization for Proton Conduction in Metal–Organic Frameworks

2021 ◽  
Author(s):  
Marvin K Sarango-Ramírez ◽  
Junkil Park ◽  
Jihan Kim ◽  
Yukihiro Yoshida ◽  
Dae-Woon Lim ◽  
...  
Keyword(s):  
Surface Functionalization ◽  
Metal Organic Frameworks ◽  
Proton Conduction ◽  
Void Space ◽  
Metal Organic

scholarly journals Void Space vs. Surface Functionalization for Proton Conduction in Metal‐Organic Frameworks

2021 ◽  
Author(s):  
Marvin K. Sarango‐Ramírez ◽  
Junkil Park ◽  
Jihan Kim ◽  
Yukihiro Yoshida ◽  
Dae‐Woon Lim ◽  
...  
Keyword(s):  
Surface Functionalization ◽  
Metal Organic Frameworks ◽  
Proton Conduction ◽  
Void Space ◽  
Metal Organic

scholarly journals Void Space vs. Surface Functionalization for Proton Conduction in Metal‐Organic Frameworks

2021 ◽  
Author(s):  
Marvin K. Sarango‐Ramírez ◽  
Junkil Park ◽  
Jihan Kim ◽  
Yukihiro Yoshida ◽  
Dae‐Woon Lim ◽  
...  
Keyword(s):  
Surface Functionalization ◽  
Metal Organic Frameworks ◽  
Proton Conduction ◽  
Void Space ◽  
Metal Organic

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>

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