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Homoleptic MOF structures of the formulas  2  ∞ [Ln( Tz* ) 3 ] and  3  ∞ [Ln( Tz* ) 3 ], ( Tz* ) –  = 1,2,3-triazolate anion, C 2 H 2 N 3  – , Ln = Gd-Lu, were obtained by the reaction of the lanthanide metals with the aromatic heterocyclic amine 1 H -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 AlCl 3  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.

zeitschrift für kristallographie - crystalline materials

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