Conformational isomerism controls collective flexibility in metal–organic framework DUT-8(Ni)

Petkov, Petko St.; Bon, Volodymyr; Hobday, Claire L.; Kuc, Agnieszka; Melix, Patrick; Kaskel, Stefan; Düren, Tina; Heine, Thomas

doi:10.1039/c8cp06600k

Cited by 46 publications

(86 citation statements)

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“…The comparison of this value with corresponding M -N bond lengths in and, shows that the value in DUT-8(Zn) is in between. The Zn-Zn-N angle is 178.65°, and comparable with that observed in DUT-8(Ni) (177.59°) (Table S1, ESI) 56. Particle sizeAs we have reported for DUT-8(Ni) and DUT-8(Co), the switching characteristics are sensitive to crystal size distribution and it was also expected for DUT-8(Zn).…”

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confidence: 85%

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Tailoring Adsorption Induced Switchability of a Pillared Layer MOF by Crystal Size Engineering

Abylgazina¹,

Senkovska²,

Ehrling

et al. 2020

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The pillared layer framework DUT-8(Zn) (Zn2(2,6-ndc)2(dabco), 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane, DUT = Dresden University of Technology) is a prototypical switchable MOF, showing characteristic adsorption and desorption induced open phase (op) to closed phase (cp) transformation associated with huge changes in cell volume. We demonstrate switchability strongly depends on a framework-specific critical particle size (dcrit). The solvent removal process (pore desolvation stress contracting the framework) significantly controls the cp/op ratio after desolvation and, subsequently, the adsorption induced switchability characteristics of the system. After desolvation, the dense cp phase of DUT-8(Zn) shows no adsorption-induced reopening and therefore is non-porous for N2 at 77 K and CO2 at 195 K. However, polar molecules with a higher adsorption enthalpy, such as the polar molecules such as chloromethane at 249 K and dichloromethane (DCM) at 298 K can reopen the macro-sized crystals upon adsorption. For macro-sized particles, the outer surface energy is negligible and only the type of metal (Zn, Co, Ni) controls the DCM-induced gate opening pressure. The framework stiffness increases from Zn to Ni as confirmed by DFT calculations, X-ray crystal structural analyses, and low frequency Raman spectroscopy. The partial disintegration of the Zn based node hinges produces an overall increased stabilization of cp vs. op phase shifts the critical particle size at which switchability starts to become suppressed to even lower values (dcrit < 200 nm) as compared to the Ni-based system (dcrit ≈ 500 nm). Hence, the three factors affecting switchability (energetics of the empty host, (Eop-Ecp) (I), particle size (II), and desolvation stress (III)) appear to be of the same order of magnitude and should be considered collectively, not individually.

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“…Crystal-downsizing was accomplished by supersaturation route, reported by Kavoosi et al in 2017 for the synthesis of rigid DUT-8(Ni) 56. All chemicals were dissolved separately: Zn(NO3)2•6H2O (446 mg, 1.5 mmol, 0.5 eq.)…”

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confidence: 99%

Tailoring Adsorption Induced Switchability of a Pillared Layer MOF by Crystal Size Engineering

Abylgazina¹,

Senkovska²,

Ehrling

et al. 2020

Preprint

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“…All simulations were carried out using GROMACS 5.1 41 with PLUMED 2.2 51 . In the case of isolated half-SBUs in solution, we investigate the structural flexibility of all three isomers as conformational isomerism is found to regulate the flexibility of the resulting framework 52 . In this context, we sample their conformational space performing WTmetaD 46 simulations using the massweighted radius of gyration (Rgyr) as a collective variable (CV).…”

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confidence: 99%

Molecular Level Understanding of the Free Energy Landscape in Early Stages of Metal–Organic Framework Nucleation

et al. 2019

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The assembly mechanism of hierarchical materials controlled by the choice of solvent and presence of spectator ions. In this paper, we use enhanced sampling molecular dynamics methods to investigate these effects on the configurational landscape of metal-linker interactions in the early stages of synthesis, using MIL-101(Cr) as a prototypical example. Microsecond-long welltempered metadynamics (WTmetaD) simulations uncover a complex free energy structural landscape, with distinct crystal (C) and non-crystal (NC) like configurations and their equilibrium population. In presence of ions (Na+, F-), we observe a complex effect on the crystallinity of secondary building units (SBUs), by encouraging/suppressing salt bridges between C configurations and consequently controlling the percentage of defects. Solvent effects are assessed by introducing N, N dimethylformamide (DMF) instead of water, where SBU adducts are appreciably more stable and compact. These results shed light on how solvent and ionic strength impact the free energy of assembly phenomena that ultimately control material synthesis

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“…A porous coordination polymer [Zn 2 (bdc) 2 (dabco)] (dabco = 1,4-diazabicyclo [2.2.2]octane) is a prototypic compound of a bountiful MOF family with highly tunable structural features [26][27][28][29][30]. We have demonstrated that the incorporation of 2,5-thiophenedicarboxylate instead of the 1,4-benzenedicarboxylate into this MOF enhances both the CO 2 adsorption uptake and the CO 2 /N 2 adsorption selectivity of [Zn 2 (tdc) 2 (dabco)] by as much as 50%, compared with the original structure [Zn 2 (bdc) 2 (dabco)] at the same conditions [31].…”

Section: Introductionmentioning

confidence: 99%

A Selenophene-Incorporated Metal–Organic Framework for Enhanced CO2 Uptake and Adsorption Selectivity

et al. 2020

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A new metal–organic coordination polymer [Zn2(sedc)2(dabco)] (1se; sedc2− = selepophene-2,5-dicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane) was synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF is based on {Zn2(OOCR)4N2} paddle wheels and is isoreticular to the family of [Zn2(bdc)2(dabco)] derivatives (1b; bdc2− = 1,4-benzenedicarboxylate) with pcu topology. The gas adsorption measurements revealed that 1se shows a 15% higher CO2 volumetric uptake at 273 K and 28% higher CO2 uptake at 298 K (both at 1 bar) compared to the prototypic framework 1b. Methane and nitrogen adsorption at 273 K was also investigated, and IAST calculations demonstrated a pronounced increase in CO2/CH4 and CO2/N2 selectivity for 1se, compared with 1b. For example, the selectivity factor for the equimolar CO2/CH4 gas mixture at 1 bar = 15.1 for 1se and 11.9 for 1b. The obtained results show a remarkable effect of the presence of selenium atom on the carbon dioxide affinity in the isoreticular metal–organic frameworks with very similar geometry and porosity.

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Conformational isomerism controls collective flexibility in metal–organic framework DUT-8(Ni)

Abstract: The linker orientation in conformational isomers of DUT-8(Ni) determines the flexibility of this metal–organic framework.

Cited by 46 publications

References 45 publications

Tailoring Adsorption Induced Switchability of a Pillared Layer MOF by Crystal Size Engineering

Tailoring Adsorption Induced Switchability of a Pillared Layer MOF by Crystal Size Engineering

Molecular Level Understanding of the Free Energy Landscape in Early Stages of Metal–Organic Framework Nucleation

A Selenophene-Incorporated Metal–Organic Framework for Enhanced CO2 Uptake and Adsorption Selectivity

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