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Zeitschrift für Kristallographie - Crystalline Materials

Editor-in-Chief: Pöttgen, Rainer

Ed. by Antipov, Evgeny / Boldyreva, Elena V. / Friese, Karen / Huppertz, Hubert / Jahn, Sandro / Tiekink, E. R. T.

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Volume 225, Issue 5


Polymorphism of isotypic series of homoleptic 1,2,3-triazolate MOFs [Ln(Tz*)3] containing the heavy lanthanides Gd–Lu: from open to dense frameworks of varying dimensionality

Jens-Christoph Rybak / Marcus Tegel / Dirk Johrendt / Klaus Müller-Buschbaum
Published Online: 2010-05-10 | DOI: https://doi.org/10.1524/zkri.2010.1242


Homoleptic MOF structures of the formulas 2[Ln(Tz*)3] and 3[Ln(Tz*)3], (Tz*) = 1,2,3-triazolate anion, C2H2N3, Ln = Gd-Lu, were obtained by the reaction of the lanthanide metals with the aromatic heterocyclic amine 1H-1,2,3-triazole. The isotypic series of compounds are real polymorphs as they have identical constitution. The 2-dimensional MOF is formed at lower temperatures whereas formation of the 3-dimensional MOF requires higher temperatures, in some cases solvothermal reaction conditions. We therefore address them as low-temperature α-form and high-temperature β-form. The thermodynamically stable β-form exhibits high thermal stabilities regarding compounds that contain three neighboring nitrogen atoms in one organic ring, ranging up to 380 °C. Transition from α to β-form is accompanied by transformation from open to dense frameworks as only the α-form contains structural voids. This goes along with both an increase of dimensionality of the linkage from 2D to 3D and an increase of the density of the structures. The α-form adopts the AlCl3 structure, the β-form can be identified with a (10,3)-b net. Although no single crystals could be obtained for β-3[Ln(Tz*)3], structure solution and reasonable refinement were successful from X-ray powder data. The crystal structure of α-2[Ln(Tz*)3] was previously solved from single crystal data.

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* Correspondence address: Ludwig-Maximilians-Universität, Department Chemie, Butenandtstr. 5-13, 81377 München, Deutschland,

Published Online: 2010-05-10

Published in Print: 2010-05-01

Citation Information: Zeitschrift für Kristallographie - Crystalline Materials, Volume 225, Issue 5, Pages 187–194, ISSN (Online) 2196-7105, ISSN (Print) 2194-4946, DOI: https://doi.org/10.1524/zkri.2010.1242.

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