Zeolitic metal azolate frameworks (MAFs) from ZnO/Zn(OH)2 and monoalkyl-substituted imidazoles and 1,2,4-triazoles: Efficient syntheses and properties

Zhu, Ai‐Xin; Lin, Rui‐Biao; Qi, Xiao‐Lin; Liang, Yan; Lin, Yan‐Yong; Zhang, Jie‐Peng; Chen, Xiaoming

doi:10.1016/j.micromeso.2011.11.033

Cited by 87 publications

(60 citation statements)

References 50 publications

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“…34 All simulations utilized the M06-2X density functional 35 coupled with the allelectron double-ζ 6-31G(d,p) basis set due to previous success. 29 Atomic positions were initialized from the experimentally determined single-crystal X-ray diffraction structure 36 and were optimized at several pressures without any symmetry constraints by adding a diagonal hydrostatic pre-stress to the analytical stress tensor. 37 It is important to note that due to ZIF-8 undergoing a phase-transition within the same space group (I43m → I43m) when using a penetrating PTM, identical results were obtained when performing simulations within the constraint of space group symmetry, as well as without any symmetry.…”

Section: Solid-state Density Functional Theorymentioning

confidence: 99%

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

et al. 2018

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The identification and characterization of low-frequency vibrational motions of metalorganic frameworks (MOFs) allows for a better understanding of their mechanical and structural response upon perturbation by external stimuli such as temperature, pressure, and adsorption. Here, we describe the combination of an experimental temperatureand pressure-dependent terahertz spectroscopy system with quantum mechanical simulations to measure and assign specific low-frequency vibrational modes that directly drive the mechanochemical properties of this important class of porous materials. More specifically, those intense spectral features in the terahertz region of the vibrational spectrum of ZIF-8 are identified, which are directly connected to its mechanochemical response. In particular, the mechanical compressibility of pristine ZIF-8 is found to follow a peculiar non-linear trend upon pressure: its bulk modulus initially increases up to 0.1 GPa and decreases at higher pressures, which is simultaneously reflected in the terahertz vibrational spectra. This work highlights the interplay between structural, vibrational, and mechanochemical phenomena, all of which are key to the effective exploitation of MOFs. The importance of terahertz vibrational motions on the function of MOFs is demonstrated, and a method presented for their measurement and interpretation, which can be applied widely to any supramolecular material.

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Section: Solid-state Density Functional Theorymentioning

confidence: 99%

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

et al. 2018

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“…It should be emphasized the lone pair electrons of the unbonded nitrogen can donate electron to the adjacent N at the 2-position, and this effect pushes the lone pair electrons of the coordinated N to bonded with the zinc center more tightly (Figure 1). The experimentallydetermined Zn-N bond length of MAF-7 (1.980(2) Å) is slightly shorter than that of ZIF-8(1.983(3) Å) at same temperature, confirming the stronger covalent interaction in the former than the latter [17]. Coordination modes of (a) imidazolate and (b) 1,2,4-triazolate; framework structures of (c) ZIF-8 and (d) MAF-7.…”

Section: Resultsmentioning

confidence: 72%

“…In the structure, the Zn 2+ ion is tetrahedrally coordinated with the triazolate ligand to form Zn(mtz)2 open framework with zeolitic sodalite (SOD) architecture. The mtz − ligand coordinates with the zinc ion via its N atoms on the 2-and 4-positions, and the N on the 1-position unbonded [16,17]. It should be emphasized the lone pair electrons of the unbonded nitrogen can donate electron to the adjacent N at the 2-position, and this effect pushes the lone pair electrons of the coordinated N to bonded with the zinc center more tightly (Figure 1).…”

Section: Resultsmentioning

confidence: 99%

Enhanced Framework Rigidity of a Zeolitic Metal-Azolate via Ligand Substitution

et al. 2017

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Abstract:The elastic properties of a zeolitic metal-azolate framework, Zn(mtz) 2 (MAF-7, mtz − = 3-methyl-1,2,4-triazolate), have been examined from the view point of the first principles calculations and experiments. Our results demonstrate that the three independent elastic constants of MAF-7 are about 5.0-73.3% higher than those of ZIF-8, though they are isomorphic. The electron-donating effect of the nitrogen atom at the 2-position in mtz-ring dominantly accounts for such a prominent difference. The detailed analysis of the full elastic tensors reveals that the volume moduli, shear moduli, and Poisson's ratios of MAF-7 are about 3.4% to 20.1%, 3.2% to 20.6%, and −30.3% to 12.3% higher than those of ZIF-8. The underlying structural reasons were discussed to explain the anisotropic difference of those properties. Moreover, the conclusion deduced from first-principle calculations was also been verified by nanoindentation and high-pressure synchrotron X-ray diffraction measurements.

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“…First hints at this conformer were obtained when inspecting powder XRD patterns of products recovered from reactions performed in aqueous ammonia. This represented a modification to previous synthetic work [39]. Inspection indicated some splitting of the most intense reflection in the powder XRD pattern of a previously discovered cubic [Zn(dcim) 2 ]-SOD material [22].…”

Section: Experimental Realization Of a Predicted Trigonal [Zn(dcim) 2mentioning

confidence: 80%

The ZIF system zinc(II) 4,5-dichoroimidazolate: theoretical and experimental investigations of the polymorphism and crystallization mechanisms

Springer

Heidenreich

Stock

et al. 2016

Zeitschrift Für Kristallographie - Crystalline Materials

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Abstract:In this report, we summarize our theoretical and experimental investigations on the zeolitic imidazolate framework (ZIF) system [Zn(dcim) 2 ] (dcim = 4,5-dichloroimidazolate) that have been published recently. These comprise: (1) a theoretical study on hypothetical conformational [Zn(dcm) 2 ]-SOD polymorphs with the same underlying sodalite (SOD) topology but distinct dcim linker orientations, (2) a synthetic work that resulted in the experimental realization of the most stable predicted (trigonal) SOD-type framework conformer and improved synthetic protocols for a previously discovered cubic SOD-type material, (3) a detailed structural analysis of the trigonal and cubic SOD-type materials, (4) a comparative characterization of the SOD-type materials by gas physisorption measurements, (5) a synthetic work that resulted in the discovery of a complete series of intermediate frameworks with the trigonal and cubic SOD-type materials as the end members, and (6) time-resolved insitu light and stopped-flow synchrotron small-angle and wide-angle X-ray scattering experiments on the rapid crystallization of the RHO-type polymorph (ZIF-71). In addition, we report as yet unpublished work, concerning time-resolved in-situ angular-dispersive synchrotron X-ray diffraction experiments on RHO-/SOD-type phase selection via the coordination modulation approach during competitive formation of the RHO-type and SOD-type materials.

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Zeolitic metal azolate frameworks (MAFs) from ZnO/Zn(OH)2 and monoalkyl-substituted imidazoles and 1,2,4-triazoles: Efficient syntheses and properties

Cited by 87 publications

References 50 publications

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

Enhanced Framework Rigidity of a Zeolitic Metal-Azolate via Ligand Substitution

The ZIF system zinc(II) 4,5-dichoroimidazolate: theoretical and experimental investigations of the polymorphism and crystallization mechanisms

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