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Issue 18, 2014
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Detection of host–guest interactions in clathrates of heterocyclic molecules adsorbed in a porous MOF with Cu2 cluster nodes via vibration spectra and magnetic properties

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Abstract

A three-dimensional NbO-type MOF with the formula Cu2(EBTC)(H2O)2·[G] (1) (EBTC4− = 1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate; G = guest molecules and represent DMF, DMSO and H2O) was synthesized using a solvothermal method. The sufficient cavity space in 1 can be used to encapsulate the heterocyclic compounds benzopyrrole (C8H7N), benzofuran (C8H6O) and benzothiophene (C8H6S). The guest-free framework (2) was obtained by heating methanol-exchanged 1 at 130 °C under vacuum. The clathrates [Cu2(EBTC)(H2O)2·1.6C8H7N] (3), [Cu2(EBTC)(H2O)2·2.5C8H6O] (4) and [Cu2(EBTC)(H2O)2·2C8H6S] (5) were prepared by soaking 2 in C8H7N, C8H6O and C8H6S at 55 °C for 48 h, respectively. 1–5 showed quite similar PXRD patterns, indicating that they have the same framework structure. The IR and Raman spectra and the variable-temperature magnetic susceptibilities were comparatively studied for 1–5; the results disclosed the existence of weakly intermolecular interactions between the –C[triple bond, length as m-dash]C– in the organic linkers and guest molecules, whereas an almost complete absence of intermolecular interactions between the paddle-wheel-type dinuclear Cu2 units and large guest molecules owing to steric hindrance. This study suggests the possibility of these rather useful MOF materials in the removal of organosulfur or organonitrogen compounds that are widely known contaminants in petroleum and fuels via their rationally designed organic linkers.

Graphical abstract: Detection of host–guest interactions in clathrates of heterocyclic molecules adsorbed in a porous MOF with Cu2 cluster nodes via vibration spectra and magnetic properties

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Article information


Submitted
13 Jan 2014
Accepted
07 Feb 2014
First published
07 Feb 2014

Dalton Trans., 2014,43, 6720-6727
Article type
Paper
Author version available

Detection of host–guest interactions in clathrates of heterocyclic molecules adsorbed in a porous MOF with Cu2 cluster nodes via vibration spectra and magnetic properties

P. Guo, T. Chen, X. Ren, C. Xiao and W. Jin, Dalton Trans., 2014, 43, 6720
DOI: 10.1039/C4DT00111G

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