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Issue 2, 2013
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Chemical transformations of a crystalline coordination polymer: a multi-stage solid–vapour reaction manifold

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Abstract

In its crystal structure the one-dimensional coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3]n (1) (TMP = 2,3,5,6-tetramethylpyrazine) adopts a zig-zag arrangement in which pairs of silver(I) centres bridged by two fluorocarboxylate ligands are linked alternately via one or two neutral TMP ligands. This material can reversibly absorb/desorb small alcohols (ROH) in single-crystal-to-single-crystal transformations, despite the lack of porosity in the crystals, to yield a related material of formula [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2]n (1-ROH). The absorption process includes coordination of the alcohol to silver(I) centres and, in the process, insertion of the alcohol into one-quarter of the Ag–O bonds of coordination polymer. When in place, the alcohol molecule is also supported by formation of an O–H⋯O hydrogen bond to the now partially dissociated carboxylate group. The reverse process leading to desorption of the alcohol takes place upon mild heating to regenerate 1. Upon further heating, 1 can release molecules of TMP into the vapour phase resulting in a separate chemical and structural transformation to yield a two-dimensional layered material of composition [Ag4(O2C(CF2)2CF3)4(TMP)2]n (2). This new transformation occurs via dissociation of Ag–N bonds upon ligand release and formation of new Ag–O bonds. The whole series of transformations has been followed in situ by single-crystal and/or powder X-ray diffraction and studied by thermogravimetric analysis. As a mechanistic probe to explore transport within formally nonporous 1, gravimetric CO2 gas sorption/desorption has been conducted. It is proposed that transport of small molecules occurs through the fluorous layers in the crystal.

Graphical abstract: Chemical transformations of a crystalline coordination polymer: a multi-stage solid–vapour reaction manifold

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Article information


Submitted
03 Oct 2012
Accepted
30 Oct 2012
First published
21 Nov 2012

Chem. Sci., 2013,4, 696-708
Article type
Edge Article

Chemical transformations of a crystalline coordination polymer: a multi-stage solid–vapour reaction manifold

I. J. Vitórica-Yrezábal, G. Mínguez Espallargas, J. Soleimannejad, A. J. Florence, A. J. Fletcher and L. Brammer, Chem. Sci., 2013, 4, 696
DOI: 10.1039/C2SC21654J

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