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Issue 13, 2018
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Direct observation of supramolecular binding of light hydrocarbons in vanadium(iii) and (iv) metal–organic framework materials

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Abstract

Fine tuning of host–guest supramolecular interactions in porous systems enables direct control over the properties of functional materials. We report here a modification of hydrogen bonding and its effect on guest binding in a pair of redox-active metal–organic frameworks (MOFs). Oxidation of MFM-300(VIII) {[VIII2(OH)2(L)], LH4 = biphenyl-3,3′,5,5′-tetracarboxylic acid} is accompanied by deprotonation of the bridging hydroxyl groups to afford isostructural MFM-300(VIV), [VIV2O2(L)]. The precise role of the hydroxyl groups, O-carboxylate centres and π–π interactions in the supramolecular binding of C2 hydrocarbons in these materials has been determined using neutron diffraction and inelastic neutron scattering, coupled with DFT modelling. The hydroxyl protons are observed to bind to adsorbed unsaturated hydrocarbons preferentially in MFM-300(VIII), particularly to C2H2, which is in a sharp contrast to MFM-300(VIV) where interactions with O-carboxylate centres and π–π interactions predominate. This variation in structure and redox leads to notably higher separation selectivity for C2H2/CH4 and C2H4/CH4 in MFM-300(VIII) than in MFM-300(VIV). Significantly, owing to the specific host–guest interactions, MFM-300(VIII) shows a record packing density for adsorbed C2H2 at 303 K and 1 bar, demonstrating its potential for use in portable acetylene stores.

Graphical abstract: Direct observation of supramolecular binding of light hydrocarbons in vanadium(iii) and (iv) metal–organic framework materials

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Supplementary files

Article information


Submitted
20 Jan 2018
Accepted
20 Feb 2018
First published
21 Feb 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 3401-3408
Article type
Edge Article

Direct observation of supramolecular binding of light hydrocarbons in vanadium(III) and (IV) metal–organic framework materials

Z. Lu, H. G. W. Godfrey, I. da Silva, Y. Cheng, M. Savage, P. Manuel, S. Rudić, A. J. Ramirez-Cuesta, S. Yang and M. Schröder, Chem. Sci., 2018, 9, 3401
DOI: 10.1039/C8SC00330K

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