4.5 Article

Base-induced formation of two magnesium metal-organic framework compounds with a bifunctional tetratopic ligand

Journal

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 23, Pages 3624-3632

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.200701284

Keywords

microporus materials; coordination polymers; metal-organic frameworks; organic-inorganic hybrid composites; adsorption; magnesium; X-ray diffraction; hydrotherrnal synthesis; 2,5-dihydroxyterepthalic acid

Funding

  1. Research Council of Norway through the NANOMAT program [153869/S10, 182056/S11]
  2. EU [NMP4-CT-2006-033335]

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Two coordination polymers constructed from magnesium and the tetratopic organic linker 2,5-dihydroxyterephithalic acid are reported, denominated CPO-26-Mg and CPO-27-Mg. The organic component carries two different types of protic functional groups, The degree of deprotonation of the organic component can be regulated by the amount of sodium hydroxide employed in the synthesis, thus determining which of the compounds forms. In CPO-26-Mg, only the carboxylic acid groups of the linker Eire deprotonated and take part in the construction of the three-dimensional framework. The structure is non-porous, and its topology is based on the PtS net. In CPO-27-Mg, both the carboxylic acid and the hydroxy groups are deprotonated and involved in the construction of a microporous three-dimensional framework which is based on a honeycomb motif containing large solvent-filled channels. The metal atoms are arranged in chiral chains along the intersection of the honeycomb and contain one water molecule in their coordination sphere, which allows for the creation of coordinatively unsaturated metal sites upon dehydration. CPO-27-Mg is a potentially useful lightweight adsorbent with a pore volume of 60 % of the total volume of the structure and an apparent Langmuir surface area of Lip to 1030 m(2)g(-1). Its thermal stability was investigated by thermogravimetry and variable-temperature powder X-ray diffraction, which shows framework degradation to commence at. 1.60 degrees C in air, at 235 degrees C under nitrogen, and at 430 degrees C in a dynamic vacuum. thermogravimetric dehydration and rehydration experiments at miscellaneous temperatures indicate that it is possible to obtain open metal sites in CPO-27-Mg, but the water is more tightly bound in this material than in the previously reported isostructural nickel compound. ((C) Wiley-VCH Verlag Gmbh & Co. KGaA, 69451 Weinheim, Germany, 2008).

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