Structural Dynamics in a “Breathing” Metal–Organic Framework Studied by Electron Paramagnetic Resonance of Nitroxide Spin Probes

Sheveleva, Alena M.; Kolokolov, Daniil I.; Gabrienko, Anton A.; Stepanov, Alexander G.; Gromilov, S. A.; Shundrina, Inna K.; Sagdeev, R. Z.; Fedin, Matvey V.; Bagryanskaya, Elena G.

doi:10.1021/jz402357v

Cited by 50 publications

(59 citation statements)

References 34 publications

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“…Recently, Bagryanskaya’s group developed an alternative approach to elucidating the generic breathing behavior of MIL-53(Al) using electron paramagnetic resonance (EPR) [123]. A very low concentration of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) was introduced as the probe (1 molecule/1,000 unit cells).…”

Section: Characterizations Of Breathing Behaviorsmentioning

confidence: 99%

A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption

2014

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Metal-organic frameworks (MOFs) are a new class of microporous materials that possess framework flexibility, large surface areas, “tailor-made” framework functionalities, and tunable pore sizes. These features empower MOFs superior performances and broader application spectra than those of zeolites and phosphine-based molecular sieves. In parallel with designing new structures and new chemistry of MOFs, the observation of unique breathing behaviors upon adsorption of gases or solvents stimulates their potential applications as host materials in gas storage for renewable energy. This has attracted intense research energy to understand the causes at the atomic level, using in situ X-ray diffraction, calorimetry, Fourier transform infrared spectroscopy, and molecular dynamics simulations. This article is developed in the following order: first to introduce the definition of MOFs and the observation of their framework flexibility. Second, synthesis routes of MOFs are summarized with the emphasis on the hydrothermal synthesis, owing to the environmental-benign and economically availability of water. Third, MOFs exhibiting breathing behaviors are summarized, followed by rationales from thermodynamic viewpoint. Subsequently, effects of various functionalities on breathing behaviors are appraised, including using post-synthetic modification routes. Finally, possible framework spatial requirements of MOFs for yielding breathing behaviors are highlighted as the design strategies for new syntheses.

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Section: Characterizations Of Breathing Behaviorsmentioning

confidence: 99%

A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption

2014

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“…A flipping motion of the aromatic rings of the linkers was separately detected in 2 H solid‐state NMR measurements . The temperature‐induced breathing and its associated hysteresis has also been detected using adsorbed nitroxides at very low concentrations: these provide a paramagnetic probe for electron paramagnetic resonance that are highly sensitive to the local environment of the guest species …”

Section: The Crystal Chemistry Of Mil‐53mentioning

confidence: 98%

MIL‐53 and its Isoreticular Analogues: a Review of the Chemistry and Structure of a Prototypical Flexible Metal‐Organic Framework

Millange

Walton

2018

Israel Journal of Chemistry

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We present a review of the structural chemistry of metal-organic framework materials with the MIL-53 type structure. This family of materials is well-known for its structural flexibility, and also the wide variety of metal cations and functional ligands that can be included. This gives rise to a set of multivariate materials and isoreticular analogues, to which isoreticular functionalisation can also be applied. Starting from the parent structure, containing infinite chains of octahedral trivalent metal cations cross-linked by benzene-1,4-dicarboxylate, we illustrate the compositional variety possible: this includes materials that contain tetravalent and divalent cations, mixtures of metal cations, functionalised ligands, expanded structures from extended linkers and inclusion of pendant ligands. We emphasise the crystal chemistry of this group of materials, but will give some examples of properties, particularly those associated with the structural breathing effect of relevance to molecular sieving, and also discuss emerging practical applications.

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“…[21][22][23][24] Because typically the porous matrix and relevant solvents are EPR-silent, this method is very suitable to track guests and species confined inside porous hosts. 22,[25][26][27] CW-EPR has already been used to study zeolithes, 28 mesoporous materials, 29,30 MOFs 31 and PMOs 21,22,32 and gave insight into the formation process, 33,34 surface polarity and surface interaction 32,35 or the dynamics of confined solutions. 22,36 Information about translational diffusion can be obtained from the Heisenberg exchange evaluation of the line broadening originating from the random collision of two dissolved radicals.…”

Section: Introductionmentioning

confidence: 99%

Multiple scale investigation of molecular diffusion inside functionalized porous hosts using a combination of magnetic resonance methods

Wessig

Spitzbarth

Drescher

et al. 2015

Phys. Chem. Chem. Phys.

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Mass transport of molecular compounds through porous solids is a decisive step in numerous, important applications like chromatography or heterogeneous catalysis. It is a multi-scale, hierarchical phenomenon: macrodiffusion (>μm) is influenced, in addition to parameters like grain boundaries and particle packing, by meso-scale (>10 nm, <μm) factors like particle size and the connectivity of pores. More importantly, meso-scale diffusion and macro-scale diffusion are first and foremost determined directly by processes on the molecular scale (<10 nm), which depend on numerous factors like pore-size, interactions of the host with the solid surfaces and with the solvent. Due to the high complexity of the latter and the fact that current analytical techniques enable only limited insights into solvent-filled pores with sufficient spatial and temporal resolution, the knowledge about the molecular origins of diffusive processes in porous materials is still restricted. The main focus of the current paper is on the development of continuous wave (CW) electron paramagnetic resonance (EPR) spectroscopy into a tool shedding some new light on molecular diffusion inside mesoporous silica materials differing systematically in pore size and surface functionalities. The advantages of CW-EPR are that its spatial resolution fits ideally to the size of mesopores (2-10 nm), it is fast enough for spotting molecular processes, and any conventional solvent and the porous matrix are EPR silent. Diffusion coefficients have been calculated considering spin exchange occurring from the diffusive collision of radicals, and are compared to complementary analytical techniques like MAS PFG NMR (sensitive for meso-scale) and EPR-imaging (sensitive to macroscale diffusion). Our results show that the choice of surface bound functional groups influences diffusion much stronger than pore-size. There are indications that this is not only due to different guest-surface interactions but also due to an altered mobility within the solvent under confinement.

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Structural Dynamics in a “Breathing” Metal–Organic Framework Studied by Electron Paramagnetic Resonance of Nitroxide Spin Probes

Cited by 50 publications

References 34 publications

A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption

A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption

MIL‐53 and its Isoreticular Analogues: a Review of the Chemistry and Structure of a Prototypical Flexible Metal‐Organic Framework

Multiple scale investigation of molecular diffusion inside functionalized porous hosts using a combination of magnetic resonance methods

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