Raman spectroscopy studies of the terahertz vibrational modes of a DUT-8 (Ni) metal–organic framework

Крылов, А. С.; Vtyurin, A. N.; Petkov, Petko St.; Senkovska, Irena; Maliuta, Mariia; Bon, Volodymyr; Heine, Thomas; Kaskel, Stefan; Slyusareva, E. A.

doi:10.1039/c7cp06225g

Cited by 60 publications

(59 citation statements)

References 46 publications

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“…Such structural oscillations in the terahertz region have been observed by Raman spectroscopy for the related MOF DUT-8. [54] The larger the system, the longer it takes for the energy in this phonon mode to dissipate. In the small system of size 3 × 3 × 3 it takes only about 200 ps until the momentum generated by the phase transition is redistributed, whereas in the largest system, there is still a significant oscillatory motion visible even 0.5 ns after the transition has finished.…”

Section: Thermal Openingmentioning

confidence: 99%

Molecular Dynamics Simulations of the “Breathing” Phase Transformation of MOF Nanocrystallites

Keupp

Schmid

2019

Advcd Theory and Sims

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Due to an error in the implementation of the analysis routine that extracts the average total potential energy ⟨U⟩ from the trajectory data, the reported values for ΔU are too small by a constant factor of 7 in the case of the periodic simulations in this manuscript. Due to this constant factor, Figures 5b and 6b are essentially identical, with, however, a scaled ordinate. The corrected figures are shown in Figure 1 and 2. As a consequence, the derived entropy contributions −TΔS to the free energy ΔA for the periodic reference case were also incorrect in the published article. The corrected Figure 6c of the original manuscript is now given in Figure 3. Due to the negligible temperature dependence of ΔU, the entropy contribution is still the dominating factor that destabilizes the cp phase at higher temperature as concluded in the original manuscript. The erroneous values for ΔU cp−op , ΔU ‡ cp−op , ΔS cp−op reported in Table S1 in the supporting information have been corrected in Table 1 and volumes for the cp and op phases were added. The Column ΔS ‡ was removed due to the absence of an entropic barrier in the corrected data.

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Section: Thermal Openingmentioning

confidence: 99%

Molecular Dynamics Simulations of the “Breathing” Phase Transformation of MOF Nanocrystallites

Keupp

Schmid

2019

Advcd Theory and Sims

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“…Motivated by its outstanding properties, DUT-8(Ni) is being investigated extensively recently. [12][13][14][15][16][17][18][19][20][21][22][23] Some examples of the properties of interest are the enormous volume change upon opening (more than 140 %), [14] its isomorphism, [22] the property dependence on the metal center, [14] and crystallite size effects. [19] Alzahrani and Deeth [24] already employed LFMM to investigate clusters of Zn 2 (bdc) 2 (dabco) and showed the applicability to this structurally related flexible MOF.…”

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confidence: 99%

A Ligand Field Molecular Mechanics Study of CO₂‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

Melix

Paesani

Heine

2019

Advcd Theory and Sims

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Flexible metal-organic Frameworks (MOFs) are an interesting class of materials due to their diverse properties. One representative of this class is the layered-pillar MOF DUT-8(Ni). This MOF consists of Ni 2 paddle wheels interconnected by naphthalene dicarboxylate linkers and dabco pillars (Ni 2 (ndc) 2 (dabco), ndc = 2,6-naphthalene-dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane). DUT-8(Ni) undergoes a volume change of over 140% upon adsorption of guest molecules. Herein, a ligand field molecular mechanics (LFMM) study of the CO 2 -induced flexibility of DUT-8(Ni) is presented. LFMM is able to reproduce experimental and DFT structural features as well as properties that require large simulation cells. It is shown that the transformation energy from a closed to open state of the MOF is overcompensated fivefold by the host-guest interactions. Structural characteristics of the MOF explain the shape of the energy profile at different loading states and provide useful insights to the interpretation of previous experimental results.the possibilities of employing ligand field molecular mechanics (LFMM) simulations to study flexible MOFs and their processes. The method employed is not limited to adsorption processes but as has been shown previously [8][9][10][11] to be applicable to other properties, for example, spin states or magnetic properties. Our goal is to present simulations using the example of CO 2induced breathing in the pillared layer MOF DUT-8(Ni) [12] (Ni 2 (ndc) 2 (dabco), ndc = 2,6naphthalenedicarboxylate, dabco = 1,4diazabicyclo-[2.2.2]-octane, see Figure 1) using an LFMM approach. Motivated by its outstanding properties, DUT-8(Ni) is being investigated extensively recently. [12][13][14][15][16][17][18][19][20][21][22][23] Some examples of the properties of interest are the enormous volume change upon opening (more than 140 %), [14] its isomorphism, [22] the property dependence on the metal center, [14] and crystallite size effects. [19] Alzahrani and Deeth [24] already employed LFMM to investigate clusters of Zn 2 (bdc) 2 (dabco) and showed the applicability to this structurally related flexible MOF. We present here the first application of LFMM to simulate the breathing of an openshell transition-metal paddle wheel pillared layer MOF in periodic boundary conditions.

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“…Finally, while this review has focused on the research of experimental groups the work of German simulation groups has provided valuable insight into flexible MOF materials. The T. Heine group has used Born-Oppenheimer molecular dynamics simulations to investigate the low-frequency lattice vibrational modes of DUT-8(Ni) [271] and illustrated that they correspond to the oscillation of the breathing mode. This group has also reported an extension to the universal forcefield [272] for treatment of MOFs structures that subsequently has been used to describe the flexibility present in these systems [273].…”

Section: Flexible Mofsmentioning

confidence: 99%

Metal–organic frameworks in Germany: From synthesis to function

Evans

Garai

Reinsch

et al. 2019

Coordination Chemistry Reviews

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102

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Metal-organic frameworks (MOFs) are constructed from a combination of inorganic and organic units to produce materials which display high porosity, among other unique and exciting properties. MOFs have shown promise in many wide ranging applications, such as catalysis and gas separations. In this review, we highlight MOF research conducted by Germany-based research groups. Specifically, we feature approaches for the synthesis of new MOFs, high-throughput MOF production, advanced characterization methods and examples of advanced functions and properties.

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Raman spectroscopy studies of the terahertz vibrational modes of a DUT-8 (Ni) metal–organic framework

Cited by 60 publications

References 46 publications

Molecular Dynamics Simulations of the “Breathing” Phase Transformation of MOF Nanocrystallites

Molecular Dynamics Simulations of the “Breathing” Phase Transformation of MOF Nanocrystallites

A Ligand Field Molecular Mechanics Study of CO₂‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

Metal–organic frameworks in Germany: From synthesis to function

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Raman spectroscopy studies of the terahertz vibrational modes of a DUT-8 (Ni) metal–organic framework

Cited by 60 publications

References 46 publications

Molecular Dynamics Simulations of the “Breathing” Phase Transformation of MOF Nanocrystallites

Molecular Dynamics Simulations of the “Breathing” Phase Transformation of MOF Nanocrystallites

A Ligand Field Molecular Mechanics Study of CO2‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)

Metal–organic frameworks in Germany: From synthesis to function

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A Ligand Field Molecular Mechanics Study of CO₂‐Induced Breathing in the Metal–Organic Framework DUT‐8(Ni)