A catenated imidazole-based coordination polymer exhibiting significant CO2 sorption at low pressure

Willans, Charlotte E.; French, Sara; Barbour, Leonard J.; Gertenbach, Jan-André; Junk, Peter Courtney; Lloyd, Gareth O.; Steed, Jonathan W.

doi:10.1039/b911265k

Cited by 22 publications

(9 citation statements)

References 22 publications

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“…Hupp and co-workers 306 reported an unusual MOF structure, 538, which was composed of metal imidazolates rather than imidazolium salts. 307 As shown in Scheme 104, the preparation of 538 was accomplished by the reaction of the tripodal imidazole compound 537 (1 equiv) and CoCl 2 •6H 2 O (1 equiv) in a solvent mixture of DMF, ethylene glycol, and pyridine at 140 °C for 72 h. The crystal structure of 538 revealed that each imidazole coordinated to one cobalt atom creating two interweaving two-dimensional sheets, which formed one-dimensional channels perpendicular to the plane with a diameter of 8.5 Å.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective

et al. 2017

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Over the course of the past 15 years the success story of N-heterocyclic carbene (NHC) compounds in organic, inorganic, and organometallic chemistry has been extended to another dimension. The immobilization of NHC compounds, undergoing continuous diversification, broadens their range of applications and leads to new solutions for challenges in catalytic and synthetic chemistry. This review intends to present a synthetic toolkit for the immobilization of NHC compounds, giving the reader an overview on synthetic techniques and strategies available in the literature. By individually summarizing and assessing the synthetic steps of the immobilization process, a comprehensive picture of the strategies and methodologies for the immobilization of NHC compounds is presented. Furthermore, the characterization of supported NHC compounds is discussed in detail in order to set up necessary criteria for an in-depth analysis of the immobilized derivatives. Finally, the catalytic applications of immobilized NHC compounds are briefly reviewed to illustrate the practical use of this technique for a broad variety of reaction types.

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Section: Chemical Reviewsmentioning

confidence: 99%

Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective

et al. 2017

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“…[102][103][104][105][106][107][108] Interestingly, when the robust solvent-free framework I was immersed into a solution of iodine in cyclohexane, its hexagonally-arranged channels allowed iodine to form very intriguing polyiodine chains. The iodine-captured framework of I, I_I 2 , was structurally characterized by X-ray crystallography ( Table 1).…”

Section: Characterization Of Current-voltage (I-v)mentioning

confidence: 99%

Thermally Robust 3-D Co-DpyDtolP-MOF with Hexagonally Oriented Micropores: Formation of Polyiodine Chains in a MOF Single Crystal

Chae

Kim

Lee

et al. 2014

Crystal Growth & Design

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A new porphyrin-based Co-MOF, [Co(DpyDtolP)] 6 ·12H 2 O (I) composed of DpyDtolP (5,15-di(4-pyridyl)-10,20-di(4-methylphenyl)porphyrin) was prepared in a high yield and structurally characterized by X-ray crystallography. DpyDtolP is a ditopic N-donor ligand with a large space or gap between the two pyridyl groups at the 5-and 15-positions of the porphyrin backbone. Unlike the pyridyl groups, the 4-tolyl groups in DpyDtolP could not be involved in coordination toward the metal ion. Nevertheless, the presence of these two 4-tolyl groups led to a new infinite three-dimensional framework: Co-MOF (I) with exceptionally high thermal stability at elevated temperature. The single crystals of I maintained their crystallinity even after vacuum drying at 250 °C. The resulting dried single crystals diffracted X-ray to give the same structural solution as the as-prepared crystals. The robust framework of I contained micropores that were periodically arranged in a hexagonal symmetry. While the evacuated I moderately sorbed N 2 at 77 K, it sorbed 142.8 cm 3 g -1 (6.37 mmol g -1 ) of CO 2 at 196 K. The CO 2 sorption isotherms exhibited a very clear step in both the adsorption and desorption branches. A slight hysteretic behavior was observed between the two branches. Furthermore, the crystal structure of CO 2 captured I (I_CO 2 ) revealed that the linear arrangement of the CO 2 molecules occupying the inside of micropores, thereby indicating the effective CO 2 capture by evacuated I.The evacuated I was also found to be ideal for the encapsulation of iodine molecules in cyclohexane to provide iodine-captured I (I_I 2 ), which was also characterized by X-ray crystallography. The linear arrangement of polyiodine chains in the micropores was observed, and a single crystal of I_I 2 exhibited electrically conducting behavior. The encapsulation amount of iodine was dependent on the crystal sizes of I. Additionally, the separately prepared microscale sample, micro-I, with a much reduced particle dimension than the bulk I exhibited an enhanced uptake of iodine under the same conditions.

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“…19 There are several members of this class of MOFs, and many of them have been reported for potential roles in interesting applications such as large, selective uptake of carbon dioxide. [20][21][22] One particularly interesting member of the ZIF family and the one investigated here is ZIF-8 (2-methylimidazole zinc salt). ZIF-8 has been demonstrated in many applications including the kinetic separation of propane/propylene, 23 the separation of hydrogen, 24 and the oxidation of CO in a ZIF-8 impregnated with gold.…”

Section: Introductionmentioning

confidence: 99%

“…ZIFs are formed by the crystallization of a transition metal species bound to the nitrogens of an imidazole compound and are so named because of their structural similarities to many zeolites (including characteristic angles of 145°, the preferred Si−O−Si angle seen in many zeolites) . There are several members of this class of MOFs, and many of them have been reported for potential roles in interesting applications such as large, selective uptake of carbon dioxide. − …”

Section: Introductionmentioning

confidence: 99%

Effects of Molecular Sieving and Electrostatic Enhancement in the Adsorption of Organic Compounds on the Zeolitic Imidazolate Framework ZIF-8

et al. 2010

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In this work, the adsorption behavior of a range of organic vapors and gases on the zeolitic imidazolate framework, ZIF-8, is investigated using an inverse gas chromatography (IGC) methodology at the zero-coverage limit and elevated temperatures. The measured thermodynamic values and surface energies for the adsorption of n-alkanes on ZIF-8 are found to be reduced from those previously reported for IRMOF-1. This reduction is most likely an effect of the predominately organic accessible surface of ZIF-8 and the resulting weaker interactions in comparison to IRMOF-1. The pore aperture size of ZIF-8, which is significantly reduced from that of IRMOF-1, is seen to introduce molecular sieving effects for branched alkanes, aromatics, and heavily halogenated compounds. Deformation polarizabilities of the adsorbates were used to calculate the specific adsorption free energy, and it is determined that the specific effects account for around 1-5 kJ/mol, or between 10% and 70% of the total free energy of adsorption for the sorbates studied (at 250 °C). The importance of electrostatic forces was seen in the significantly enhanced adsorption of propylene and ethylene in comparison to their respective alkanes and in the direct correlation shown between the specific components of the free energy of adsorption and the adsorbate's dipole moment.

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A catenated imidazole-based coordination polymer exhibiting significant CO2 sorption at low pressure

Abstract: A robust, porous, catenated coordination polymer based on a neutral, flexible imidazole-derived tripodal ligand (a 'tripodal imidazole framework', TIF) reversibly absorbs vapours and gases, particularly CO2.

Cited by 22 publications

References 22 publications

Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective

Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective

Thermally Robust 3-D Co-DpyDtolP-MOF with Hexagonally Oriented Micropores: Formation of Polyiodine Chains in a MOF Single Crystal

Effects of Molecular Sieving and Electrostatic Enhancement in the Adsorption of Organic Compounds on the Zeolitic Imidazolate Framework ZIF-8

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