cg3009249_si_003.cif (10.89 kB)

Porous Metal–Organic Frameworks with Multiple Cages Based on Tetrazolate Ligands: Synthesis, Structures, Photoluminescence, and Gas Adsorption Properties

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posted on 06.02.2013 by Tien-Wen Tseng, Tzuoo-Tsair Luo, She-Yu Chen, Chong-Cheng Su, Kai-Ming Chi, Kuang-Lieh Lu
Three tetrazolate-based coordination polymers [Mn­(TzA)­(H2O)2]n (1, H2TzA = 1H-tetrazole-5-acetic acid), {[Cd5(MTz)9]·OH}n (2, MTz = 5-methyltetrazolate), and [Cd3(MTz)3Cl3]n (3) were synthesized via the reactions of a tetrazole ligand H2TzA with metal ions under hydrothermal conditions. During the formation of 2 and 3, Cd­(II) ions were coordinated by MTz, which was generated as the result of the in situ decarboxylation of the H2TzA ligand. Single-crystal X-ray diffraction analyses revealed that 1 possessed an infinite 2D layer structure with a μ3-TzA2– moiety, forming a 44-sql topology, and the 2D sheets were further hydrogen-bonded to form a 3D framework. Compound 2 had a 3D porous framework with a 49·66-acs topology. Compound 3 adopted a 3D porous framework with a body-centered cubic (bcu) topology, which was comprised of 48-membered (Cd24Cl24) rings, and it demonstrated a moderate adsorption of H2 over N2 as a result of its limited window size. The solid-state luminescent properties of complexes 2 and 3 and the corresponding HMTz molecule were also investigated.

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