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Influence of the substitution pattern of four naphthalenedicarboxylic acids on the structures and properties of group 13 metal–organic frameworks and coordination polymers

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Abstract

Metal–organic frameworks containing Ga3+ ions and four differently substituted naphthalenedicarboxylates (ndc2−) have been synthesized and characterized. The Ga3+ ions are six-fold coordinated by oxygen atoms in all title compounds, but two different inorganic building units, i.e. trans corner-sharing and cis,trans edge-sharing octahedra are observed. Crystal structures were validated by Rietveld refinements against powder X-ray diffraction data. [Ga(OH)(1,4-ndc)]·2H2O crystallizes in a non-breathing MIL-53 type structure with two different pore sizes (5.5 × 5.5 Å and 9 × 9 Å). It is non-porous with respect to nitrogen but has a water adsorption capacity of about 155 mg g−1 and a thermal stability of up to 240 °C. The dense compound [Ga(OH)(1,8-ndc)] crystallizes in a new layered structure motif, which is related to the crystal structure of MIL-122 ([Al(OH)((O2C)4C6H2)]). The third and fourth compounds [Ga2(OH)4(2,3-ndc)]·H2O and [Ga(OH)(2,6-ndc)]·H2O are isoreticular to CAU-15 ([Al2(OH)4(2,3-bdc)]·H2O) and MIL-69 ([Al(OH)(2,6-ndc)]·H2O), respectively. The last two compounds are non-porous toward nitrogen but reversible dehydration was demonstrated. For comparison, the two new compounds [Al(OH)(1,8-ndc)] and [Al2(OH)4(2,3-ndc)]·H2O, which are isostructural to the newly described gallium compounds, were also synthesized and fully characterized. The Al-containing coordination polymers exhibit higher temperature stabilities compared to their isostructural Ga compounds.

Graphical abstract: Influence of the substitution pattern of four naphthalenedicarboxylic acids on the structures and properties of group 13 metal–organic frameworks and coordination polymers

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Supplementary files

Article information


Submitted
03 Feb 2020
Accepted
17 Mar 2020
First published
20 Mar 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Influence of the substitution pattern of four naphthalenedicarboxylic acids on the structures and properties of group 13 metal–organic frameworks and coordination polymers

T. Rabe, H. Pewe, H. Reinsch, T. Willhammar, E. Svensson Grape and N. Stock, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT00387E

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