In Situ X‐ray Structural Studies of a Flexible Host Responding to Incremental Gas Loading

Jacobs, Tia; Lloyd, Gareth O.; Gertenbach, Jan-André; Müller-Nedebock, Kristian K.; Esterhuysen, Catharine; Barbour, Leonard J.

doi:10.1002/anie.201201281

Cited by 67 publications

(48 citation statements)

References 44 publications

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“…84 A unique approach was recently applied by Barbour and coworkers. 90 Three states, were modeled using DFT simulations; an empty metallocycle, a metallocycle with one guest and a metallocycle with two guests (the maximum occupancy). The resulting interaction energies, obtained from these simulations, were used to construct of a statistical model to give total occupancy as a function of pressure.…”

Section: Gas Adsorptionmentioning

confidence: 99%

Application of computational methods to the design and characterisation of porous molecular materials

et al. 2017

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Composed from discete units, porous molecular materials (PMMs) possess unique properties not observed for conventional, extended, solids, such as solution processibility and permanent porosity in the liquid phase. However, identifying the origin of porosity is not a trivial process, especially for amorphous or liquid phases. Furthermore, the assembly of molecular components is typically governed by a subtle balance of weak intermolecular forces that makes structure prediction challenging. Accordingly, in this review we canvass the crucial role of molecular simulations in the characterisation and design of PMMs. We will outline strategies for modelling porosity in crystalline, amorphous and liquid phases and also describe the state-of-the-art methods used for high-throughput screening of large datasets to identify materials that exhibit novel performance characteristics.

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Section: Gas Adsorptionmentioning

confidence: 99%

Application of computational methods to the design and characterisation of porous molecular materials

et al. 2017

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“…Barbour and his co-workers reported a series of [M 2 Cl 4 bi 2 ]·2CH 3 OH (M = Cd, Zn and Co), which each complex the two metal ions are tetrahedrally coordinated to two chloride anions and two C-shaped bridging ligands. Metallocycles stack to form columns, and that this packing mode creates solvent-filled pockets between adjacent metallocycles [17][18]. Each metallocycle shares cavities with both of its neighbors.…”

Section: [Cu(l) 2 (Bib)(h 2 O) 2 ] N (2)mentioning

confidence: 99%

Two new 1D coordination polymers: syntheses, structures and properties

Wu¹,

Wang²,

Liu³

et al. 2014

Bull. Chem. Soc. Eth.

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ABSTRACT. Two new coordination polymers, namely, [Zn(bi)(Cl)2]n (1) and [Cu(L)2(bib)(H2O)2]n (2) (bi = 4,4'-bis(2-methylimidazol-1-ylmethyl)biphenyl; L = 4-(2-(4-(methoxycarbonyl)phenoxy)ethoxy)benzoic acid and bib = 2,3-bis(4-pyridyl)butane), are synthesized and characterized. Both of 1 and 2 have 1D covalent chains, which show different conformally chain feature. 2D supremolecular rhombic and rectangle motifs are observed in 1 and 2, respectively. The O-H···O and C-H···Cl hydrogen-bonding interactions play a significant role in promoting the diversity of structural patterns.

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“…However, the crystallographic observation of adsorbed gas adsorbents generally has not been possible due to the poor crystalline order of adsorbents upon removing residual solvent/guest molecules and the high mobility of gases even at low temperatures. Only a limited number of gas-adsorbed single-crystal structures have been determined at low temperatures (16,(28)(29)(30)(31)(32)(33)(34)(35)(36).…”

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confidence: 99%

High-temperature in situ crystallographic observation of reversible gas sorption in impermeable organic cages

Baek

Moon

Graf

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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Crystallographic observation of adsorbed gas molecules is a highly difficult task due to their rapid motion. Here, we report the in situ single-crystal and synchrotron powder X-ray observations of reversible CO 2 sorption processes in an apparently nonporous organic crystal under varying pressures at high temperatures. The host material is formed by hydrogen bond network between 1,3,5-tris-(4-carboxyphenyl)benzene (H 3 BTB) and N,N-dimethylformamide (DMF) and by π-π stacking between the H 3 BTB moieties. The material can be viewed as a well-ordered array of cages, which are tight packed with each other so that the cages are inaccessible from outside. Thus, the host is practically nonporous. Despite the absence of permanent pathways connecting the empty cages, they are permeable to CO 2 at high temperatures due to thermally activated molecular gating, and the weakly confined CO 2 molecules in the cages allow direct detection by in situ single-crystal X-ray diffraction at 323 K. Variable-temperature in situ synchrotron powder X-ray diffraction studies also show that the CO 2 sorption is reversible and driven by temperature increase. Solid-state magic angle spinning NMR defines the interactions of CO 2 with the organic framework and dynamic motion of CO 2 in cages. The reversible sorption is attributed to the dynamic motion of the DMF molecules combined with the axial motions/angular fluctuations of CO 2 (a series of transient opening/closing of compartments enabling CO 2 molecule passage), as revealed from NMR and simulations. This temperature-driven transient molecular gating can store gaseous molecules in ordered arrays toward unique collective properties and release them for ready use.in situ X-ray diffraction | nonporous organic crystalline material | CO 2 sorption G uest capture, storage, and removal in porous materials have been interesting topics in chemistry (1-7). The porosity of solids is one of the important factors determining their potential applications in guest storage. Because the storage generally uses void spaces interconnected through large open channels between the voids inside the crystal, nonporous or seemingly nonporous materials have received less attention. Over the past decades, nevertheless, due to the potential for selective guest capture and release in a controlled manner there have been attempts to study such materials which include calixarenes (8-17), 4-phenoxyphenol (18), biconcave molecules (19), tris(5-acetyl-3-thienyl)methane (20), metallocyclic complex (21), clarithromycin (22), and metalorganic frameworks (23, 24).Single-crystal X-ray diffraction can provide the crucial information on the binding interactions or structural changes of guest molecules within pores (25-27). However, the crystallographic observation of adsorbed gas adsorbents generally has not been possible due to the poor crystalline order of adsorbents upon removing residual solvent/guest molecules and the high mobility of gases even at low temperatures. Only a limited number of gas-adsorbed single-crystal struct...

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In Situ X‐ray Structural Studies of a Flexible Host Responding to Incremental Gas Loading

Cited by 67 publications

References 44 publications

Application of computational methods to the design and characterisation of porous molecular materials

Application of computational methods to the design and characterisation of porous molecular materials

Two new 1D coordination polymers: syntheses, structures and properties

High-temperature in situ crystallographic observation of reversible gas sorption in impermeable organic cages

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